Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a seri...Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a series of double network self-healing(DN_(SA))hydrogels based on hydrophobic association and ionic bond were prepared for plugging pores and fractures in formations in oil and gas drilling and production engineering.The mechanical,rheological,and self-healing properties of the DN_(SA)hydrogels were investigated.Results revealed that the DN_(SA)hydrogels exhibited excellent mechanical properties with a tensile stress of 0.67 MPa and toughness of 7069 kJ/cm^(3) owing to the synergistic effect of the double network.In addition,the DN_(SA)hydrogels exhibited excellent compression resistance,notch insensitivity,and self-healing properties.The DN_(SA)-2 hydrogel was granulated and made into gel particles with different particle sizes and used as a plugging agent.The self-healing mechanism of DN_(SA)-2 hydrogel particles in fractures was explored,and it’s plugging effect on fractures of different widths and porous media of different permeabilities were investigated.Experimental results revealed that the plugging capacity of the DN_(SA)-2 hydrogel particles for a fracture with width of 5 mm and a porous medium with a permeability of 30μm^(2) was 3.45 and 4.21 MPa,respectively,which is significantly higher than those of commonly used plugging agents in the oilfield.The DN_(SA)hydrogels with excellent mechanical and self-healing properties prepared in this study will provide a new approach for applying hydrogels in oil and gas drilling and production engineering.展开更多
Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the se...Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the separation of m-cresol from cumene and n-heptane by liquid–liquid extraction using ionic liquids(ILs) as extractants was studied. The suitable ILs were screened by conductor-like screening model for real solvents(COSMO-RS)model and the liquid–liquid phase equilibrium(LLE) experiments were to verify the accuracy of the screening results. The extraction conditions such as extraction time, extraction temperature and mass ratio of ILs to model oils were evaluated. An internal mechanism of the m-cresol extract by ILs was revealed by COSMO-RS calculation and FT-IR. The results showed that the selected ILs can extract m-cresol effectively from cumene and nheptane, 1-ethyl-3-methylimidazolium acetate(emim CH3 COO) was the best extraction solvent. A hydrogen bond between anion of ILs and phenolic hydroxyl groups was observed. M-cresol in model oils could be extracted with extraction efficiencies up to 98.85% at an emim CH3 COO: model oils mass ratio of 0.5 and 298.15 K,emim CH3 COO could be regenerated and reused for 4 cycles without obvious decreases in extraction efficiency and extractant mass.展开更多
Some expressions were proposed in the previous report to exp-ress the relation between the entropies S°<sub>298</sub> and the bond parameterZ/r in the same type of compounds.Based on this we derived a...Some expressions were proposed in the previous report to exp-ress the relation between the entropies S°<sub>298</sub> and the bond parameterZ/r in the same type of compounds.Based on this we derived a rela-tion formula for calculating the ionic entropies and established a展开更多
The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of th...The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.展开更多
Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, ...Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.展开更多
Novel Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0-0.8)ceramics,designed by replacing Ce^(4+)with Yb^(3+)ions were prepared by conventional oxide reaction,and the structural stability of the cubic fluorite structure was assessed usin...Novel Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0-0.8)ceramics,designed by replacing Ce^(4+)with Yb^(3+)ions were prepared by conventional oxide reaction,and the structural stability of the cubic fluorite structure was assessed using lattice energy and ionic properties of Ce/Yb-O bonds.The oxygen vacancy caused by unequal substitution,which played a decisive role in bond ionicity and lattice energy,was analyzed experimentally by XPS and also theoretically by first principles.The Yb_(x)Ce_(1-x)O_(2-0.5x) ceramics maintain a stable cubic fluorite structure when x≤0.47,corresponding to the minimum lattice energy of 4142 kJ/mol with the lowest ionicity as ƒ_(i)=87.57%.For microwave dielectric properties,when the Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0-0.4)ceramics are pure phase,the porosity-corrected permittivity is dependent on the bond ionicity.The Q׃ values are related to the lattice energy and grain distribution.The temperature coefficient of resonance frequency has been analyzed using bond valence.When the Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0.5-0.8)ceramics are multiple phases,the microwave dielectric properties are associated with the phase composition and grain growth.展开更多
Phenolic compounds exist in crude oil as pollutants, and their removal is vital important for the refining and further application of oils. In traditional separation approaches, strong acid and strong base have to be ...Phenolic compounds exist in crude oil as pollutants, and their removal is vital important for the refining and further application of oils. In traditional separation approaches, strong acid and strong base have to be used to remove these compounds, which may cause serious environmental problems. In this work, 19 kinds of cholinium ionic liquids have been developed to separate phenol from model oil by liquid–liquid extraction. Structural effect of anions of the ionic liquids in the separation is systematically investigated. It is found that depending on the chemical structure of ionic liquids, phenol can be removed from toluene with single-step removal efficiency from 86 to 99% under optimal conditions. The type of substituent groups and the-CH_2 number between two carboxylates have obvious effect on the removal efficiency, and more hydrophilic ionic liquids have a stronger extraction performance for phenol. Furthermore, thermodynamic,^(13) C NMR,~1 H NMR and density functional theory calculations have been performed to characterize the extraction process and to understand the extraction mechanism. It is shown that the extraction of phenol from oil to ionic liquid is a favorable process, and this process is mainly driven by enthalpy change. The formation of the hydrogen bond between anion of the ionic liquid and-OH of phenol is the main driving force for the extraction of phenol from oil to the ionic liquids.展开更多
Recently ionic liquids(ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial & error a...Recently ionic liquids(ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial & error as well as selection based on existing literature are the methods currently employed for selecting and/or tuning ILs. These methods are probabilistic, time consuming, expensive and may not result in selecting high performance ILs for gas hydrate mitigation. In this work, COSMO-RS is considered as a prescreening tool of ILs for gas hydrate mitigation by predicting the hydrogen bonding energies(E_(HB)) of studied IL inhibitors and comparing the predicted E_(HB) to the depression temperature(?) and induction time. Results show that, predicted EHBand chain length of ILs strongly relate and significantly affect the gas hydrate inhibition depression temperature but correlate moderately(R = 0.70) with average induction time in literature. It is deduced from the results that, ? increases with increasing IL EHBand/or decreases with increasing chain length. However, the cation–anion pairing of ILs also affects IL gas hydrate inhibition performance. Furthermore, a visual and better understanding of IL/water behavior for gas hydrate inhibition in terms of hydrogen bond donor and acceptor interaction analysis is also presented by determining the sigma profile and sigma potential of studied IL cations and anions used for gas hydrate mitigation for easy IL selection.展开更多
In recent years, one of the priority areas of research in chemistry has become the processes carried out in an environment of liquid organic salts, the so-called ionic liquids (ILs), which are assessed as environmenta...In recent years, one of the priority areas of research in chemistry has become the processes carried out in an environment of liquid organic salts, the so-called ionic liquids (ILs), which are assessed as environmentally friendly or “green” alternatives to conventional organic solvents. ILs are non-volatile, highly polar solvents that dissolve many organic, inorganic, and organometallic compounds. Since they have no detectable vapor pressure, ILs are considered as potential substitutes for volatile organic compounds traditionally used as solvents. So-called deep eutectic solvents (DES) is a group of ILs that are liquid mixtures of a number of organic and (or) inorganic components taken in a certain ratio (eutectic or close to eutectic). DES deserve a special attention due to their negligible saturated vapor pressure, availability, low cost, as well as ability to dissolve at relatively high concentration of metal salts, metal oxides and various polymers. Particularly DES based on a mixture of choline chloride with urea (DES-1) or a mixture of choline chloride and adduct of urea with hydrogen peroxide (DES-2) give eutectics that are liquid at ambient temperature and have unusual solvent properties, including an ability to dissolve an animal hair in the presence of low concentration of sodium sulfide or ammonium thioglycolate. It was found that depending on the ratio between DES-1 and DES-2 in the mixture of two Deep Eutectic Solvents and the nature of sulfur-containing additive, the solubility of rabbit hair under used conditions, varies from 51% to 79%.展开更多
The ionic transport process in polymer electrolytes (such as polyethylene oxide) wassimulated numerically on a two dimensional square lattice where charge carriers areaccommodated by the lattice sites connected random...The ionic transport process in polymer electrolytes (such as polyethylene oxide) wassimulated numerically on a two dimensional square lattice where charge carriers areaccommodated by the lattice sites connected randomly with available bonds to represent theamorphous chain configuration. Following the dynamic bond percolation theory(DBPT),the chainmotion contribution to the ionic conduction was incorporated via periodical renewal of the randombond configuration. To check and extend the prediction made by DBPT employing global abruptbond renewal,spatial correlation of the bond reassignment was introduced to the system by: 1)regional bond renewal and 2) organized bond motion. It is found that the difference between thediffusivities simulated involving regional bond renewal and those of DBPT becomes negligiblewhen the bond renewal rate approaches the carrier hopping rate.展开更多
Carbon forms a variety of compounds with single, double, triple and the intermediate resonance bonds with atoms of its own or other kinds. This paper is concerned with graphite, a very useful material, which is a stac...Carbon forms a variety of compounds with single, double, triple and the intermediate resonance bonds with atoms of its own or other kinds. This paper is concerned with graphite, a very useful material, which is a stack of electrically conducting graphene layers held together by weak van der Waals (vdW) bonds. It crystallizes in hexagonal and rhombohedral forms, in which the hexagon inter-planar bond distance is 0.34 nm. Here a new and simple approach accounts for this bond length and shows the coulombic nature of the vdW bond.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.52074327 and 51991361)。
文摘Self-healing hydrogels have attracted tremendous attention in the field of oil and gas drilling and production engineering because of their excellent self-healing performance after physical damage.In this study,a series of double network self-healing(DN_(SA))hydrogels based on hydrophobic association and ionic bond were prepared for plugging pores and fractures in formations in oil and gas drilling and production engineering.The mechanical,rheological,and self-healing properties of the DN_(SA)hydrogels were investigated.Results revealed that the DN_(SA)hydrogels exhibited excellent mechanical properties with a tensile stress of 0.67 MPa and toughness of 7069 kJ/cm^(3) owing to the synergistic effect of the double network.In addition,the DN_(SA)hydrogels exhibited excellent compression resistance,notch insensitivity,and self-healing properties.The DN_(SA)-2 hydrogel was granulated and made into gel particles with different particle sizes and used as a plugging agent.The self-healing mechanism of DN_(SA)-2 hydrogel particles in fractures was explored,and it’s plugging effect on fractures of different widths and porous media of different permeabilities were investigated.Experimental results revealed that the plugging capacity of the DN_(SA)-2 hydrogel particles for a fracture with width of 5 mm and a porous medium with a permeability of 30μm^(2) was 3.45 and 4.21 MPa,respectively,which is significantly higher than those of commonly used plugging agents in the oilfield.The DN_(SA)hydrogels with excellent mechanical and self-healing properties prepared in this study will provide a new approach for applying hydrogels in oil and gas drilling and production engineering.
基金Supported by the National Key Projects for Fundamental Research and Development of China(2016YFB0600305).
文摘Low temperature coal tar contained a large amount of phenols, aromatic hydrocarbons and alkanes;the separation of phenols from coal tar has a great significance to the deep processing of coal tar. In this work, the separation of m-cresol from cumene and n-heptane by liquid–liquid extraction using ionic liquids(ILs) as extractants was studied. The suitable ILs were screened by conductor-like screening model for real solvents(COSMO-RS)model and the liquid–liquid phase equilibrium(LLE) experiments were to verify the accuracy of the screening results. The extraction conditions such as extraction time, extraction temperature and mass ratio of ILs to model oils were evaluated. An internal mechanism of the m-cresol extract by ILs was revealed by COSMO-RS calculation and FT-IR. The results showed that the selected ILs can extract m-cresol effectively from cumene and nheptane, 1-ethyl-3-methylimidazolium acetate(emim CH3 COO) was the best extraction solvent. A hydrogen bond between anion of ILs and phenolic hydroxyl groups was observed. M-cresol in model oils could be extracted with extraction efficiencies up to 98.85% at an emim CH3 COO: model oils mass ratio of 0.5 and 298.15 K,emim CH3 COO could be regenerated and reused for 4 cycles without obvious decreases in extraction efficiency and extractant mass.
文摘Some expressions were proposed in the previous report to exp-ress the relation between the entropies S°<sub>298</sub> and the bond parameterZ/r in the same type of compounds.Based on this we derived a rela-tion formula for calculating the ionic entropies and established a
基金This work was supported by the National Natural Science Key Foundation of China (20490209) and Young Teacher Foundation of Beijing Chemical Technology University (QN0308)
文摘The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.
文摘Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.
基金the Fundamental Research Funds for the Central Universities(Grant No.2020ZDPYMS12).
文摘Novel Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0-0.8)ceramics,designed by replacing Ce^(4+)with Yb^(3+)ions were prepared by conventional oxide reaction,and the structural stability of the cubic fluorite structure was assessed using lattice energy and ionic properties of Ce/Yb-O bonds.The oxygen vacancy caused by unequal substitution,which played a decisive role in bond ionicity and lattice energy,was analyzed experimentally by XPS and also theoretically by first principles.The Yb_(x)Ce_(1-x)O_(2-0.5x) ceramics maintain a stable cubic fluorite structure when x≤0.47,corresponding to the minimum lattice energy of 4142 kJ/mol with the lowest ionicity as ƒ_(i)=87.57%.For microwave dielectric properties,when the Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0-0.4)ceramics are pure phase,the porosity-corrected permittivity is dependent on the bond ionicity.The Q׃ values are related to the lattice energy and grain distribution.The temperature coefficient of resonance frequency has been analyzed using bond valence.When the Yb_(x)Ce_(1-x)O_(2-0.5x)(x=0.5-0.8)ceramics are multiple phases,the microwave dielectric properties are associated with the phase composition and grain growth.
基金supported by the National Natural Science Foundation of China(No.21803017,21733011)the National Key Research and Development Program of China(2017YFA0403101)+2 种基金S&T Research Foundation of Education Department of Henan Province(No.19A150027)the 111 project(No.D17007)the Open Research Fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes
文摘Phenolic compounds exist in crude oil as pollutants, and their removal is vital important for the refining and further application of oils. In traditional separation approaches, strong acid and strong base have to be used to remove these compounds, which may cause serious environmental problems. In this work, 19 kinds of cholinium ionic liquids have been developed to separate phenol from model oil by liquid–liquid extraction. Structural effect of anions of the ionic liquids in the separation is systematically investigated. It is found that depending on the chemical structure of ionic liquids, phenol can be removed from toluene with single-step removal efficiency from 86 to 99% under optimal conditions. The type of substituent groups and the-CH_2 number between two carboxylates have obvious effect on the removal efficiency, and more hydrophilic ionic liquids have a stronger extraction performance for phenol. Furthermore, thermodynamic,^(13) C NMR,~1 H NMR and density functional theory calculations have been performed to characterize the extraction process and to understand the extraction mechanism. It is shown that the extraction of phenol from oil to ionic liquid is a favorable process, and this process is mainly driven by enthalpy change. The formation of the hydrogen bond between anion of the ionic liquid and-OH of phenol is the main driving force for the extraction of phenol from oil to the ionic liquids.
文摘Recently ionic liquids(ILs) are introduced as novel dual function gas hydrate inhibitors. However, no desired gas hydrate inhibition has been reported due to poor IL selection and/or tuning method. Trial & error as well as selection based on existing literature are the methods currently employed for selecting and/or tuning ILs. These methods are probabilistic, time consuming, expensive and may not result in selecting high performance ILs for gas hydrate mitigation. In this work, COSMO-RS is considered as a prescreening tool of ILs for gas hydrate mitigation by predicting the hydrogen bonding energies(E_(HB)) of studied IL inhibitors and comparing the predicted E_(HB) to the depression temperature(?) and induction time. Results show that, predicted EHBand chain length of ILs strongly relate and significantly affect the gas hydrate inhibition depression temperature but correlate moderately(R = 0.70) with average induction time in literature. It is deduced from the results that, ? increases with increasing IL EHBand/or decreases with increasing chain length. However, the cation–anion pairing of ILs also affects IL gas hydrate inhibition performance. Furthermore, a visual and better understanding of IL/water behavior for gas hydrate inhibition in terms of hydrogen bond donor and acceptor interaction analysis is also presented by determining the sigma profile and sigma potential of studied IL cations and anions used for gas hydrate mitigation for easy IL selection.
文摘In recent years, one of the priority areas of research in chemistry has become the processes carried out in an environment of liquid organic salts, the so-called ionic liquids (ILs), which are assessed as environmentally friendly or “green” alternatives to conventional organic solvents. ILs are non-volatile, highly polar solvents that dissolve many organic, inorganic, and organometallic compounds. Since they have no detectable vapor pressure, ILs are considered as potential substitutes for volatile organic compounds traditionally used as solvents. So-called deep eutectic solvents (DES) is a group of ILs that are liquid mixtures of a number of organic and (or) inorganic components taken in a certain ratio (eutectic or close to eutectic). DES deserve a special attention due to their negligible saturated vapor pressure, availability, low cost, as well as ability to dissolve at relatively high concentration of metal salts, metal oxides and various polymers. Particularly DES based on a mixture of choline chloride with urea (DES-1) or a mixture of choline chloride and adduct of urea with hydrogen peroxide (DES-2) give eutectics that are liquid at ambient temperature and have unusual solvent properties, including an ability to dissolve an animal hair in the presence of low concentration of sodium sulfide or ammonium thioglycolate. It was found that depending on the ratio between DES-1 and DES-2 in the mixture of two Deep Eutectic Solvents and the nature of sulfur-containing additive, the solubility of rabbit hair under used conditions, varies from 51% to 79%.
文摘The ionic transport process in polymer electrolytes (such as polyethylene oxide) wassimulated numerically on a two dimensional square lattice where charge carriers areaccommodated by the lattice sites connected randomly with available bonds to represent theamorphous chain configuration. Following the dynamic bond percolation theory(DBPT),the chainmotion contribution to the ionic conduction was incorporated via periodical renewal of the randombond configuration. To check and extend the prediction made by DBPT employing global abruptbond renewal,spatial correlation of the bond reassignment was introduced to the system by: 1)regional bond renewal and 2) organized bond motion. It is found that the difference between thediffusivities simulated involving regional bond renewal and those of DBPT becomes negligiblewhen the bond renewal rate approaches the carrier hopping rate.
文摘Carbon forms a variety of compounds with single, double, triple and the intermediate resonance bonds with atoms of its own or other kinds. This paper is concerned with graphite, a very useful material, which is a stack of electrically conducting graphene layers held together by weak van der Waals (vdW) bonds. It crystallizes in hexagonal and rhombohedral forms, in which the hexagon inter-planar bond distance is 0.34 nm. Here a new and simple approach accounts for this bond length and shows the coulombic nature of the vdW bond.
