During the development of shale gas,various issues such as low individual well production,rapid decline,limited reservoir control,and low recovery rates have arisen.Enhancing shale gas reservoir recovery rates has con...During the development of shale gas,various issues such as low individual well production,rapid decline,limited reservoir control,and low recovery rates have arisen.Enhancing shale gas reservoir recovery rates has consistently been a focal point and challenge within the industry.Therefore,this paper employs molecular dynamic(MD)simulation methods to study the adsorption and diffusion characteristics of CH_(4)/CO_(2)at different temperatures and mixing ratios.It compares the effects of temperature and CH_(4)/CO_(2)molar ratio changes on the selectivity coefficient,adsorption capacity,and diffusion coefficient of CH_(4)/CO_(2).The paper also plots the displacement interface and the function of CH_(4)/CO_(2)injection/residual amounts over time.Furthermore,it analyzes the adsorption capacity of molecules on the graphene surface,the migration capacity of molecules in the slit,and the displacement process of CH_(4)by CO_(2)on the nanoscale,revealing the microscopic mechanism of CH_(4)/CO_(2)competitive adsorption and displacement.The research results indicate that the influence of temperature on the selectivity coefficient is not significant,with an average decrease of 3%for every 20 K rise in temperature.Pressure has a more pronounced effect on the selectivity coefficient,with values around 1.4 at low pressures and around 1.2 at high pressures.Elevating the mole fraction of CO_(2)in the binary gas mixture results in an increase in the total adsorption amount and an accelerated variation of adsorption amount with pressure.As the CH_(4)mole fraction rises,the diffusion coefficient of CH_(4)increases,while the diffusion coefficient of CO_(2)diminishes with an increasing CO_(2)mole fraction.Under identical conditions,CO_(2)exhibits a stronger adsorption capacity over CH_(4)in shale organic nanopores,resulting in a concave moon-shaped displacement interface in the model.The larger the pre-adsorption pressure of CO_(2),the more intense the movement of CO_(2)along the graphene surface,and the faster the diffusion speed of CO_(2)along the wall.In a displacement pore(the pore space used to provide the displacement location or site)with a diameter of 3 nm,at smaller pressure differentials(≤10 MPa),the residual amount of CH_(4)remains relatively stable without substantial alteration.However,at a pressure differential of 20 MPa,the residual amount of CH_(4)decreases rapidly,and the displacement efficiency significantly improves.展开更多
Converting peanut shells into biochar by pyrolysis was considered an environmentally friendly and efficient method for agricultural solid waste disposal.The properties of peanut shell-derived biochar(PBC)under differe...Converting peanut shells into biochar by pyrolysis was considered an environmentally friendly and efficient method for agricultural solid waste disposal.The properties of peanut shell-derived biochar(PBC)under different temperature and its adsorption capacity of heavy metals were investigated.It was found that PBC400 exhibited the highest cumulative capability for heavy metals elimination in single solute because of its high specific surface area and rich functional groups.Furthermore,the competitive adsorption revealed that PBC had a substantial difference in adsorption affinity from diverse heavy metal ions,sorption capacity decreased as Pb2+>Cu2+>Cd2+>Ni2+>Zn2+,which was lower than in a single solute.The adsorption process using selected biochar was optimized with respect to p H,reaction time,adsorbent dose,and initial concentration of heavy metals.The kinetic data was well fitted with PSO model,and the Langmuir model was adopted for adsorption equilibrium data in both cases of single solutes and mixed solutes for all heavy metals,which indicated that the removal course was primarily explained by monolayer adsorption,and chemical adsorption occupied an important role.Therefore,peanut shells derived biochar could be a potential and green adsorbent for wastewater treatment.展开更多
An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1 amino 2 naphthol 4 sulfonic acid(1, 2, 4 acid) and 2 naphthol obtained from various bin...An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1 amino 2 naphthol 4 sulfonic acid(1, 2, 4 acid) and 2 naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for 1, 2, 4 acid was an endothermic process in comparison with that for 2 naphthol of an exothermic process. 2 naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4 acid. However, the adsorption to 1, 2, 4 acid depressed that to 2 naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4 acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4 acid based on the larger selectivity index.展开更多
The adsorption amount, ξ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer （FDN） and STPP. The experimental results s...The adsorption amount, ξ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer （FDN） and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g （about 72.5%）. The adsorption amount of FDN was reduced by STPP, but ξ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca^2＋ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ξ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.展开更多
A new competitive adsorption isothermal model(CAIM)was developed for the coexistent and competitive binding of heavy metals to the soil surface.This model extended the earlier adsorption isothermal models by consideri...A new competitive adsorption isothermal model(CAIM)was developed for the coexistent and competitive binding of heavy metals to the soil surface.This model extended the earlier adsorption isothermal models by considering more than one kind of ion adsorption on the soil surface.It was compared with the Langmuir model using different conditions, and it was found that CAIM,which was suitable for competitive ion adsorption at the soil solid-liquid surface,had more advantages than the Langmuir model.The new competitive adsorption isothermal model was used to fit the data of heavy metal(Zn and Cd)competitive adsorption by a yellow soil at two temperatures.The results showed that CAIM was appropriate for the competitive adsorption of heavy metals on the soil surface at different temperatures.The fitted parameters of CAIM had explicit physical meaning.The model allowed for the calculation of the standard molar Gibbs free energy change,the standard molar enthalpy change,and the standard molar entropy change of the competitive adsorption of the heavy metals,Zn and Cd,by the yellow soil at two temperatures using the thermodynamic equilibrium constants.展开更多
Fe3O4-octadecyltrichlorosilane（Fe3O4-OTS）was synthesized and used to remove dyes in a competitive system.Fe3O4-OTS was prepared by slow hydrolysis of OTS in cyclohexane on the surface of Fe3O4obtained through coprec...Fe3O4-octadecyltrichlorosilane（Fe3O4-OTS）was synthesized and used to remove dyes in a competitive system.Fe3O4-OTS was prepared by slow hydrolysis of OTS in cyclohexane on the surface of Fe3O4obtained through coprecipitation method.Scanning electron microscope（SEM）,energy dispersive spectrometer（EDS）,and contact angle analyzer（CA）were used to analyze the properties of Fe3O4-OTS.Methyl orange（MO）and methylene blue（MB）were selected as model molecules to study the influence mechanism of p H and ionic strength on competitive adsorption.The results of EDS and CA indicated that Fe3O4 was modified successfully with OTS on the surface.Silicon appeared and carbon content increased obviously on the surface of adsorbent.Contact angle of adsorbent increased from 0~o to 107~o after being modified by OTS.Fe3O4-OTS showed good separation for MO and MB in competitive system,which has potential to separate dyes in sewage.Separation factor（β~OB）changed from 18.724 to 0.017,when p H changed from 7 to 12,revealing that MO and MB could be separated almost thoroughly by Fe3O4-OTS.p H could change the surface charge of Fe3O4-OTS and structure of dyes,and thus change the interactions of competitive system indirectly.Even though hydrophobic interaction was enhanced,ionic strength reduced the difference of electrostatic interaction between dyes and Fe3O4-OTS.So it is unfavorable to separate dyes with opposite charges when ionic strength increases.These findings may provide theoretical guidances to separate two-component dye pollutants.展开更多
The uptake capacities, and the adsorption kinetics, of copper, Cu（Ⅱ）, nickel, Ni（Ⅱ）, and cadmium, Cd（Ⅱ）, on peat have been studied under static conditions. The results show that the adsorption rates are rapid...The uptake capacities, and the adsorption kinetics, of copper, Cu（Ⅱ）, nickel, Ni（Ⅱ）, and cadmium, Cd（Ⅱ）, on peat have been studied under static conditions. The results show that the adsorption rates are rapid： equilibrium is reached in twenty minutes. The adsorption of copper, nickel and cadmium is pH dependent over the pH range from 2 to 6. The adsorption kinetics can be excellently described by the Elovich kinetic equation. The adsorption isotherm fits a Langmuir model very well. The adsorption capacities follow the order Cu^2＋ 〉 Ni^2＋〉 Cd^2＋ in single-component systems and the competitive adsorption capacities fall in the decreasing order Cu^2＋ 〉 Ni^2＋〉 Cd^2＋ in multi-component systems. The adsorption capacities of these three heavy metal ions on peat are consistent with their observed competitive adsorption capacities.展开更多
To establish a theoretical foundation for simultaneous removal of multi-heavy metals,the adsorption of Cu（Ⅱ） and Pb（Ⅱ） ions from their single and binary systems by Ca-alginate immobilized activated carbon and Sa...To establish a theoretical foundation for simultaneous removal of multi-heavy metals,the adsorption of Cu（Ⅱ） and Pb（Ⅱ） ions from their single and binary systems by Ca-alginate immobilized activated carbon and Saccharomyces cerevisiae （CAS） was investigated.The CAS beads were characterized by Scanning electron microscope （SEM） and Fourier transformed infrared spectroscopy （FTTR）.The effect of initial pH,adsorbent dosage,contact time and initial metal ions concentration on the adsorption process was systematically investigated.The experimental maximum contents of Cu（Ⅱ） and Pb（Ⅱ） uptake capacity were determined as 64.90 and 166.31 mg/g,respectively.The pseudo-second-order rate equation and Langmuir isotherm model could explain respectively the kinetic and isotherm experimental data of Cu（Ⅱ） and Pb（Ⅱ） ions in single-component systems with much satisfaction.The experimental adsorption data of Cu（Ⅱ） and Pb（Ⅱ） ions in binary system were best described by the extended Freundlich isotherm and the extended Langmuir isotherm,respectively.The removal of Cu（lⅡ） ions was more significantly influenced by the presence of the coexistent Pb（Ⅱ） species,while the Pb（Ⅱ） removal was affected slightly by varying the initial concentration of Cu（Ⅱ）.The CAS was successfully regenerated using 1 mol/L HNO3 solution.展开更多
Heavy metals can be introduced into urban soils at the same time. Therefore, their selective retention and competitive adsorption by the soils become of major importance in determining their availability and movement ...Heavy metals can be introduced into urban soils at the same time. Therefore, their selective retention and competitive adsorption by the soils become of major importance in determining their availability and movement throughout the soil. In this study, the availability and mobility of six heavy metals in eight urban soils collected from different cities of Zhejiang Province, southeastern China were assessed using distribution coefficients（Kd） and retardation factor（Rf）. The results showed that there were great differences in the Kd and Rfamong the tested soils. The adsorption sequences were Cr〉Pb〉Cu〉Cd〉Zn〉Ni, and the Kd decreased with increasing levels of metal addition. Ni generally has the lowest Rf values followed closely by Cd, and Zn whereas Cr and Pb reached the highest values. The results suggest that Ni and Zn have the highest mobility associated to the lowest adsorption, Cr and Pb present the opposite behavior. Correlation analysis indicates that soil pH, CaCO3 content, and cation exchange capacity （CEC） are key factors controlling the solubility and mobility of the metals in the urban soils.展开更多
Soils can often be contaminated simultaneously by more than one heavy metal. The sorption-desorption behavior of a metal in a soil will be affected by the presence of other metals. Therefore, selective retention and c...Soils can often be contaminated simultaneously by more than one heavy metal. The sorption-desorption behavior of a metal in a soil will be affected by the presence of other metals. Therefore, selective retention and competitive adsorption of the soils to heavy metals can affect their availability and movement through the soils. In this study, the simultaneous competitive adsorption of four heavy metals (Cd, Cu, Hg, and Pb) on ten agricultural soils collected from the Changjiang and Zhujiang deltas, China was assessed. The results showed that the competition affected the behavior of heavy metal cations in such a way that the soils adsorbed less Cd and Hg, and more Pb and Cu with increasing total metal concentrations, regardless of the molar concen- tration applied. As the applied concentrations increased, Pb and Cu adsorption increased, while Cd and Hg adsorption decreased. The adsorption sequence most found was Pb>Cu>Hg>Cd. The maximum adsorption capacity for the heavy metal cations was calculated, and affected markedly by soil properties. The results suggest that Hg and Cd have higher mobility associated to the lower adsorption and that Pb and Cu present the opposite behavior. Significant correlations were found between the maximum adsorption capacity of the metals and pH value and exchangeable acid, suggesting that soil pH and exchangeable acid were key factors controlling the solubility and mobility of the metals in the agricultural soils.展开更多
To compare the adsorption kinetics of Cu, Zn and Cd introduced into red soils simultaneously and sequentially as well as their distribution coefficients, the ability of red soils to retain heavy metals was evaluated b...To compare the adsorption kinetics of Cu, Zn and Cd introduced into red soils simultaneously and sequentially as well as their distribution coefficients, the ability of red soils to retain heavy metals was evaluated by performing batch experiments. The results indicate that Cu is preferentially adsorbed by red soils no matter in simultaneous or in sequential situation. The adsorption amount of Cd is the minimum in simultaneous competitive adsorption experiment. As heavy metals are added into red soils sequentially, the heavy metal adsorptions are relatively hard to reach equilibrium in 2 h. Red soils retain more Cd than Zn, which is opposite to the result in simultaneous adsorption. The addition sequences of heavy metals affect their adsorbed amounts in red soils to a certain extent. The joint distribution coefficients of metals in simultaneous adsorption are slightly higher than those in sequential adsorption.展开更多
Competition of hydrocarbon compounds with sulfides in gasoline has caused a not very high selectivity of sulfides in adsorption desulfurization so far,resulting in a reduction of catalyst lifetime as well as more sulf...Competition of hydrocarbon compounds with sulfides in gasoline has caused a not very high selectivity of sulfides in adsorption desulfurization so far,resulting in a reduction of catalyst lifetime as well as more sulfur oxide emissions.Tostudy the whole competitive process changing with the increase of the loading,the dynamic competition adsorption mechanism of cyclohexene and thiophene in siliceous faujasite(FAU)zeolite was analyzed by the Monte Carlo simulation.The results showed that with the increase of the loading,thiophene and cyclohexene had different performances before and after the inflection point of 40 molecule/UC.The adsorbates were distributed ideally at optimal sites during the stage that occurred before the inflection point,which is called the“optimal-displacement adsorption”stage.When approaching the inflection point,the competition became apparent and the displacement appeared accordingly,some thiophene molecules at S sites(refers to the sites inside the supercages)were displaced by cyclohexene.After the inflection point,the concentration of adsorbates at W sites(refers to the 12-membered ring connecting the supercages)was significantly reduced,whereas the adsorbates at S sites got more concentrated.The stage some cyclohexene molecules displaced by thiophene and inserted into the center of the supercage can be named as the“insertion-displacement adsorption”stage,and both the adsorption behavior and the competitive relationship became localized when the adsorption amount became saturated.This shift in the competitive adsorption mechanism was due to the sharp increase of interaction energy between the adsorbates.Besides,the increase in temperature and ratio of Si/Al will allow the adsorbates,especially thiophene molecules to occupy more adsorption sites,and it is beneficial to improve the desulfurization selectivity.展开更多
Atomic force microscopy (AFM) was used to study the competitive adsorption betweenbovine serum albumin (BSA) and type Ⅰ collagen on hydrophilic and hydrophobic silicon wafers.BSA showed a grain shape and the type Ⅰ ...Atomic force microscopy (AFM) was used to study the competitive adsorption betweenbovine serum albumin (BSA) and type Ⅰ collagen on hydrophilic and hydrophobic silicon wafers.BSA showed a grain shape and the type Ⅰ collagen displayed fibril-like molecules with relativelyhomogeneous height and width, characterized with clear twisting (helical formation). These AFMimages illustrated that quite a lot of type Ⅰ collagen appeared in the adsorption layer on hydrophilicsurface in a competitive adsorption state, but the adsorption of BSA was more preponderant than thatof type Ⅰ collagen on hydrophobic silicon wafer surface. The experiments showed that theinfluence of BSA on type Ⅰ collagen adsorption on hydrophilic surface was less than that onhydrophobic surface.展开更多
Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the flu...Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the fluidity of mortar decreased sharply,so it should be used together with a superplasticizer to enable good workability.With its powerful charge density in the molecular structure,the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process.Consequently,we experimentally studied on the bleeding rate and rheological properties of cement slurry,fluidity and mechanical properties of mortar with welan gum mixed with superplasticizer,aiming at understanding the competitive adsorption phenomenon by application of welan gum mixed with superplasticizer.By measuring the hydration heat and zeta potential,the mechanism of interaction of welan gum with superplasticizer was deduced and explained.The results showed that it could ensure a good dispersion effect when welan gum is mixed with the two kinds of superplasticizer.Welan gum had little impact on the naphthalene superplasticizer,but did have a substantial influence on polycarboxylate.In practice,adding welan gum after PCE acted with cement for 2 min could effectively avoid the competitive adsorption and then achieve better performance.On this viewpoint for mortar with PCE,new delay release welan gum needs further research and development.展开更多
The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures includ...The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures included benzene/toluene, toluene/xylene, benzene/isopropylbenzene, ethyl acetate/toluene and benzene/ethyl acetate. Experimental results show that various ACF-Ps, as with ACF-W, can remove both vapors in binary vapor mixtures with over 99% of removal efficiency before the breakthrough point of the more weakly adsorbed vapor. In dynamic competitive adsorption, the more weakly adsorbed vapor not only penetrates early, but also will be displaced and desorbed consequently by stronger adsorbate and therefore produces a rolling up in the breakthrough curve. The ACF-Ps prepared at different temperatures have somewhat different adsorption selectivity. The feed concentration ratio of vapors, the length/diameter ratio and the thick of bed have effect on competitive adsorption. The competitive adsorption ability of a vapor is mainly related to its boiling point. Usually, the higher the boiling point, the stronger the vapor adsorbed on ACF-P.展开更多
An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS)...An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS).In this study,the competitive adsorption and diffusion mechanism of two systems,diethyl sulfide/cyclohexene and n-butyl mercaptan/cyclohexene,with different adsorption amounts in siliceous faujasite zeolite(FAU) were investigated by Monte Carlo(MC) and molecular dynamics(MD).The systems exhibited a two-stage loading-dependent competitive adsorption and diffusion mechanism,with an inflection point of 32 molecule/UC(moleculers per microcoulomb).Before the inflection point(4-32molecule/UC),the competition mechanism of the two systems was the "optimal-displacement" mechanism.After the inflection point,the mechanism of the diethyl sulfide/cyclohexene changed to "relocation-displacement",while that of the n-butyl mercaptan/cyclohexene system changed to "dominantdisplacement".Compared to ether functional groups,the alcohol functional group has higher polarity and stronger adsorption stability,thus occupying more favorable adsorption sites within the supercages(SCs),while ethyl sulfide shifts outward to other sites within other SCs.In addition,the diffusion performance of adsorbent is related to the adsorption energy.The lower the adsorption energy,the weaker the diffusion ability.Meanwhile,the diffusion performance of adsorbates is better at high temperatures and low adsorption capacity.The effect of temperatu re on the desulfu rization selectivity was determined.A lower temperature is favorable for the adsorption capacity of the two systems and the removal selectivity of sulfides.This study provides fundamental insights into the competitive adsorption and diffusion mechanisms among sulfides,mercaptans and olefins,offering theoretical guidance for adsorbent design and reaction temperature optimization.展开更多
This study mainly investigates the influence of pore water characteristics on the adsorption properties of coalbed methane through integrated low field nuclear magnetic resonance(LF-NMR),adsorption experiments,and mol...This study mainly investigates the influence of pore water characteristics on the adsorption properties of coalbed methane through integrated low field nuclear magnetic resonance(LF-NMR),adsorption experiments,and molecular dynamics(MD)simulations.Pore water states in three coal ranks were characterized during progressive hydration.Multi-scale analysis revealed how pore water evolution regulates methane adsorption processes.During the diffusion-dominated stage(M2-M3),adsorbed water penetrates into the micropores.In the highly wettable brown coal(L1),the adsorbed water content reaches 2.12 g while in the anthracite(A1),it is only 0.29 g.During the active water injection stage(M4-M6),non-adsorbed water dominates in anthracite(over 85%of the total water content of 4.01 g),while adsorbed water remains dominant in lignite(over 60%of the total water content of 3.52 g).Water content plays a key role in methane adsorption in coal.During the water addition phase,the influence of methane adsorption on medium-to-low-rank coal is relatively weak,while the methane adsorption capacity of high-rank coal A1 shows a significant decrease during both the water diffusion and water addition phases,corresponding to a reduction in Langmuir volume of 21.22 cm^(3)/g.Molecular dynamics(MD)results further show that the free energy between molecules on the surface of hydroxyl-modified coal increases,with hydroxyl groups driving electrostatic interactions between coal and water molecules.Increased steric hindrance inhibits hydrogen bond formation and reduces the rate of hydrogen bond growth.There is a significant correlation between pore water content and coal-water molecular interaction energy,which cross-scale validates the results of LF-NMR testing and MD simulations.展开更多
As the fundamental unit of soil,aggregates exhibit significant variations in their abilities to adsorb and desorb trace elements,depending on their size.Batch experiments were conducted to investigate the characterist...As the fundamental unit of soil,aggregates exhibit significant variations in their abilities to adsorb and desorb trace elements,depending on their size.Batch experiments were conducted to investigate the characteristics of adsorption and desorption of cadmium(Cd),copper(Cu),and lead(Pb)on and from soil aggregate fractions from three layers of a calcareous soil profile in Changxing County,Zhejiang Prvince,China.The results showed that both Langmuir and Freundlich models successfully described the isothermal adsorption processes of single Cd,Cu,and Pb on different soil aggregates.Additionally,aggregates from the bottom soil layer showed the highest maximum adsorption capacity and required the lowest energy for Cd,Cu,and Pb adsorption compared to aggregates from upper soil layers.The physicochemical properties of soil aggregates were found to govern the adsorption and desorption processes of heavy metals rather than the aggregate size,wherein the contents of iron/aluminum oxides and organic matter were the most crucial influencing factors.Cadmium displayed higher mobility than Cu and Pb in different soil aggregates,and the maximum adsorption capacities of the metal ions followed the order of Pb>Cu>Cd,while their desorption rates followed the order of Cd>Cu>Pb.Additionally,the<0.053 mm microaggregates presented the lowest desorption rates for Cd,Cu,and Pb compared to other soil aggregate fractions in each soil layer.Furthermore,the orthogonal experiment results demonstrated that the competitive adsorption between metals occurred on soil aggregates in the ternary heavy metal system,but only the desorption of Pb was significantly affected by the coexistence of Cd and Cu.展开更多
The competitive adsorption and desorption of Pb（II） and Cu（II） ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 tool. L^-1 CaC12 as background elec...The competitive adsorption and desorption of Pb（II） and Cu（II） ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 tool. L^-1 CaC12 as background electrolyte. The desorption isotherms of Pb（lI） and Cu（II） were similar to the adsorption isotherms, which can be fitted well by Freundlich equation （R2 〉 0.96）. The soil in the three sites had greater sorption capacities for Pb（II） than Cu （II）, which was affected strongly by the soil characteristics. In the binary metal solution containing 1 ： 1 molar ratio of Pb（II） and Cu（II）, the total amount of Pb（II） and Cu（lI） adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared （FT-IR） spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.展开更多
Shale gas is an unconventional gas source with substantial development potential.In this study,Longmaxi Formation shale from the Silurian system in Yibin,Sichuan Province was collected for characterizing total organic...Shale gas is an unconventional gas source with substantial development potential.In this study,Longmaxi Formation shale from the Silurian system in Yibin,Sichuan Province was collected for characterizing total organic carbon(TOC),clay mineral content,and other reservoir properties.The pore structure of shale was analyzed by field-emission scanning electron microscopy and low-temperature N_(2) adsorption–desorption method.Isothermal adsorption experiments for CH_(4)and CO_(2)mixtures in shale samples were performed.The second Virial coefficient was used to calculate for the compressibility factor of the gas mixture.The influencing factors of gas adsorption capacity of shale were analyzed.Finally,the CH_(4)and CO_(2)adsorption capacities and selection of shale samples were investigated.Under low pressure,the total gas mixture capacity of shale samples was positively correlated with pressure.When the pressure increased to a certain extent,the growth trend of gas mixture adsorption capacity of shale samples decreased.The mixed gas adsorption volume is high at 50℃ for all the proportion.Given the same temperature and pressure,the CO_(2)adsorption of shale samples is higher than the CH_(4)adsorption.In competitive adsorption,shale prefers to adsorb CO_(2).Therefore,CO_(2)is easier to be adsorbed by shale and this causes CH_(4)to be released from the adsorption site.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.52222402,52234003 and 52074235)Sichuan Science and Technology Program(NO:2022JDJQ0009 and No.2023NSFSC0934)+2 种基金the Science and Technology Cooperation Project of the CNPC-SWPU Innovation Alliance(Grant No.2020CX020202)the Deep Marine Shale Gas Efficient Development Overseas Expertise Introduction Center for Discipline Innovation(111 Center)the China Postdoctoral Science Foundation(Grant No.2022M722638).
文摘During the development of shale gas,various issues such as low individual well production,rapid decline,limited reservoir control,and low recovery rates have arisen.Enhancing shale gas reservoir recovery rates has consistently been a focal point and challenge within the industry.Therefore,this paper employs molecular dynamic(MD)simulation methods to study the adsorption and diffusion characteristics of CH_(4)/CO_(2)at different temperatures and mixing ratios.It compares the effects of temperature and CH_(4)/CO_(2)molar ratio changes on the selectivity coefficient,adsorption capacity,and diffusion coefficient of CH_(4)/CO_(2).The paper also plots the displacement interface and the function of CH_(4)/CO_(2)injection/residual amounts over time.Furthermore,it analyzes the adsorption capacity of molecules on the graphene surface,the migration capacity of molecules in the slit,and the displacement process of CH_(4)by CO_(2)on the nanoscale,revealing the microscopic mechanism of CH_(4)/CO_(2)competitive adsorption and displacement.The research results indicate that the influence of temperature on the selectivity coefficient is not significant,with an average decrease of 3%for every 20 K rise in temperature.Pressure has a more pronounced effect on the selectivity coefficient,with values around 1.4 at low pressures and around 1.2 at high pressures.Elevating the mole fraction of CO_(2)in the binary gas mixture results in an increase in the total adsorption amount and an accelerated variation of adsorption amount with pressure.As the CH_(4)mole fraction rises,the diffusion coefficient of CH_(4)increases,while the diffusion coefficient of CO_(2)diminishes with an increasing CO_(2)mole fraction.Under identical conditions,CO_(2)exhibits a stronger adsorption capacity over CH_(4)in shale organic nanopores,resulting in a concave moon-shaped displacement interface in the model.The larger the pre-adsorption pressure of CO_(2),the more intense the movement of CO_(2)along the graphene surface,and the faster the diffusion speed of CO_(2)along the wall.In a displacement pore(the pore space used to provide the displacement location or site)with a diameter of 3 nm,at smaller pressure differentials(≤10 MPa),the residual amount of CH_(4)remains relatively stable without substantial alteration.However,at a pressure differential of 20 MPa,the residual amount of CH_(4)decreases rapidly,and the displacement efficiency significantly improves.
基金financially supported by State’s Key Project of Research and Development Plan,China(y804091001)National Natural Science Foundation of China(51776211)Key Special Project for Introduced Talents Team of Southern Marine Science and Engineering Guangdong Laboratory(Guangzhou)(GML2019ZD0101)。
文摘Converting peanut shells into biochar by pyrolysis was considered an environmentally friendly and efficient method for agricultural solid waste disposal.The properties of peanut shell-derived biochar(PBC)under different temperature and its adsorption capacity of heavy metals were investigated.It was found that PBC400 exhibited the highest cumulative capability for heavy metals elimination in single solute because of its high specific surface area and rich functional groups.Furthermore,the competitive adsorption revealed that PBC had a substantial difference in adsorption affinity from diverse heavy metal ions,sorption capacity decreased as Pb2+>Cu2+>Cd2+>Ni2+>Zn2+,which was lower than in a single solute.The adsorption process using selected biochar was optimized with respect to p H,reaction time,adsorbent dose,and initial concentration of heavy metals.The kinetic data was well fitted with PSO model,and the Langmuir model was adopted for adsorption equilibrium data in both cases of single solutes and mixed solutes for all heavy metals,which indicated that the removal course was primarily explained by monolayer adsorption,and chemical adsorption occupied an important role.Therefore,peanut shells derived biochar could be a potential and green adsorbent for wastewater treatment.
文摘An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1 amino 2 naphthol 4 sulfonic acid(1, 2, 4 acid) and 2 naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for 1, 2, 4 acid was an endothermic process in comparison with that for 2 naphthol of an exothermic process. 2 naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4 acid. However, the adsorption to 1, 2, 4 acid depressed that to 2 naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4 acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4 acid based on the larger selectivity index.
基金Funded by the National Basic Research Program of China(973 Program)(2009CB23201)the National Natural Science Foundation of China(51378408)the Fundamental Research Funds for the Central Universities of China(WUT:2013-IV-036)
文摘The adsorption amount, ξ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer （FDN） and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g （about 72.5%）. The adsorption amount of FDN was reduced by STPP, but ξ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca^2＋ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ξ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.
基金Project supported by the Program for Changjiang Scholars and Innovative Research Team in University of China(No.IRT0749)
文摘A new competitive adsorption isothermal model(CAIM)was developed for the coexistent and competitive binding of heavy metals to the soil surface.This model extended the earlier adsorption isothermal models by considering more than one kind of ion adsorption on the soil surface.It was compared with the Langmuir model using different conditions, and it was found that CAIM,which was suitable for competitive ion adsorption at the soil solid-liquid surface,had more advantages than the Langmuir model.The new competitive adsorption isothermal model was used to fit the data of heavy metal(Zn and Cd)competitive adsorption by a yellow soil at two temperatures.The results showed that CAIM was appropriate for the competitive adsorption of heavy metals on the soil surface at different temperatures.The fitted parameters of CAIM had explicit physical meaning.The model allowed for the calculation of the standard molar Gibbs free energy change,the standard molar enthalpy change,and the standard molar entropy change of the competitive adsorption of the heavy metals,Zn and Cd,by the yellow soil at two temperatures using the thermodynamic equilibrium constants.
基金Funded by the National Natural Science Foundation of China(Nos.51403229,21401209,and U1507104)the Foundation of Youth Innovation Promotion Association,CAS(Y310031024)+1 种基金the Natural Science Foundation of Qinghai Province(2015-ZJ-933Q)the West Light Foundation of CAS
文摘Fe3O4-octadecyltrichlorosilane（Fe3O4-OTS）was synthesized and used to remove dyes in a competitive system.Fe3O4-OTS was prepared by slow hydrolysis of OTS in cyclohexane on the surface of Fe3O4obtained through coprecipitation method.Scanning electron microscope（SEM）,energy dispersive spectrometer（EDS）,and contact angle analyzer（CA）were used to analyze the properties of Fe3O4-OTS.Methyl orange（MO）and methylene blue（MB）were selected as model molecules to study the influence mechanism of p H and ionic strength on competitive adsorption.The results of EDS and CA indicated that Fe3O4 was modified successfully with OTS on the surface.Silicon appeared and carbon content increased obviously on the surface of adsorbent.Contact angle of adsorbent increased from 0~o to 107~o after being modified by OTS.Fe3O4-OTS showed good separation for MO and MB in competitive system,which has potential to separate dyes in sewage.Separation factor（β~OB）changed from 18.724 to 0.017,when p H changed from 7 to 12,revealing that MO and MB could be separated almost thoroughly by Fe3O4-OTS.p H could change the surface charge of Fe3O4-OTS and structure of dyes,and thus change the interactions of competitive system indirectly.Even though hydrophobic interaction was enhanced,ionic strength reduced the difference of electrostatic interaction between dyes and Fe3O4-OTS.So it is unfavorable to separate dyes with opposite charges when ionic strength increases.These findings may provide theoretical guidances to separate two-component dye pollutants.
基金Project[2006]331 supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education of China0504 by the Doctoral Initial Foundation of East China University of Technology070712 by the Initial Foundation by Key Laboratory of Nuclear Resources and Environment,Ministry of Education of China
文摘The uptake capacities, and the adsorption kinetics, of copper, Cu（Ⅱ）, nickel, Ni（Ⅱ）, and cadmium, Cd（Ⅱ）, on peat have been studied under static conditions. The results show that the adsorption rates are rapid： equilibrium is reached in twenty minutes. The adsorption of copper, nickel and cadmium is pH dependent over the pH range from 2 to 6. The adsorption kinetics can be excellently described by the Elovich kinetic equation. The adsorption isotherm fits a Langmuir model very well. The adsorption capacities follow the order Cu^2＋ 〉 Ni^2＋〉 Cd^2＋ in single-component systems and the competitive adsorption capacities fall in the decreasing order Cu^2＋ 〉 Ni^2＋〉 Cd^2＋ in multi-component systems. The adsorption capacities of these three heavy metal ions on peat are consistent with their observed competitive adsorption capacities.
基金Project(11JJ2031)supported by the Key Project of Natural Science Foundation of Hunan Province,China
文摘To establish a theoretical foundation for simultaneous removal of multi-heavy metals,the adsorption of Cu（Ⅱ） and Pb（Ⅱ） ions from their single and binary systems by Ca-alginate immobilized activated carbon and Saccharomyces cerevisiae （CAS） was investigated.The CAS beads were characterized by Scanning electron microscope （SEM） and Fourier transformed infrared spectroscopy （FTTR）.The effect of initial pH,adsorbent dosage,contact time and initial metal ions concentration on the adsorption process was systematically investigated.The experimental maximum contents of Cu（Ⅱ） and Pb（Ⅱ） uptake capacity were determined as 64.90 and 166.31 mg/g,respectively.The pseudo-second-order rate equation and Langmuir isotherm model could explain respectively the kinetic and isotherm experimental data of Cu（Ⅱ） and Pb（Ⅱ） ions in single-component systems with much satisfaction.The experimental adsorption data of Cu（Ⅱ） and Pb（Ⅱ） ions in binary system were best described by the extended Freundlich isotherm and the extended Langmuir isotherm,respectively.The removal of Cu（lⅡ） ions was more significantly influenced by the presence of the coexistent Pb（Ⅱ） species,while the Pb（Ⅱ） removal was affected slightly by varying the initial concentration of Cu（Ⅱ）.The CAS was successfully regenerated using 1 mol/L HNO3 solution.
文摘Heavy metals can be introduced into urban soils at the same time. Therefore, their selective retention and competitive adsorption by the soils become of major importance in determining their availability and movement throughout the soil. In this study, the availability and mobility of six heavy metals in eight urban soils collected from different cities of Zhejiang Province, southeastern China were assessed using distribution coefficients（Kd） and retardation factor（Rf）. The results showed that there were great differences in the Kd and Rfamong the tested soils. The adsorption sequences were Cr〉Pb〉Cu〉Cd〉Zn〉Ni, and the Kd decreased with increasing levels of metal addition. Ni generally has the lowest Rf values followed closely by Cd, and Zn whereas Cr and Pb reached the highest values. The results suggest that Ni and Zn have the highest mobility associated to the lowest adsorption, Cr and Pb present the opposite behavior. Correlation analysis indicates that soil pH, CaCO3 content, and cation exchange capacity （CEC） are key factors controlling the solubility and mobility of the metals in the urban soils.
基金Project supported by the National Basic Research Program (973) of China (Nos. 2005CB121104 and 2002CB410804)the National Natural Science Foundation of China (No. 40471064)the Natural Science Foundation of Zhejiang Province (No. R306011), China
文摘Soils can often be contaminated simultaneously by more than one heavy metal. The sorption-desorption behavior of a metal in a soil will be affected by the presence of other metals. Therefore, selective retention and competitive adsorption of the soils to heavy metals can affect their availability and movement through the soils. In this study, the simultaneous competitive adsorption of four heavy metals (Cd, Cu, Hg, and Pb) on ten agricultural soils collected from the Changjiang and Zhujiang deltas, China was assessed. The results showed that the competition affected the behavior of heavy metal cations in such a way that the soils adsorbed less Cd and Hg, and more Pb and Cu with increasing total metal concentrations, regardless of the molar concen- tration applied. As the applied concentrations increased, Pb and Cu adsorption increased, while Cd and Hg adsorption decreased. The adsorption sequence most found was Pb>Cu>Hg>Cd. The maximum adsorption capacity for the heavy metal cations was calculated, and affected markedly by soil properties. The results suggest that Hg and Cd have higher mobility associated to the lower adsorption and that Pb and Cu present the opposite behavior. Significant correlations were found between the maximum adsorption capacity of the metals and pH value and exchangeable acid, suggesting that soil pH and exchangeable acid were key factors controlling the solubility and mobility of the metals in the agricultural soils.
基金Projects(40971179,41271294)supported by the National Natural Science Foundation of ChinaProject(NCET-09-330)supported by the Program for New Century Excellent Talents in University,ChinaProject(11JJ3041)supported by the Natural Science Foundation of Hunan Province,China
文摘To compare the adsorption kinetics of Cu, Zn and Cd introduced into red soils simultaneously and sequentially as well as their distribution coefficients, the ability of red soils to retain heavy metals was evaluated by performing batch experiments. The results indicate that Cu is preferentially adsorbed by red soils no matter in simultaneous or in sequential situation. The adsorption amount of Cd is the minimum in simultaneous competitive adsorption experiment. As heavy metals are added into red soils sequentially, the heavy metal adsorptions are relatively hard to reach equilibrium in 2 h. Red soils retain more Cd than Zn, which is opposite to the result in simultaneous adsorption. The addition sequences of heavy metals affect their adsorbed amounts in red soils to a certain extent. The joint distribution coefficients of metals in simultaneous adsorption are slightly higher than those in sequential adsorption.
基金the National Natural Science Foundation of China(21822810,21838011)the National Key Research and Development Program(2018YFC1902603).
文摘Competition of hydrocarbon compounds with sulfides in gasoline has caused a not very high selectivity of sulfides in adsorption desulfurization so far,resulting in a reduction of catalyst lifetime as well as more sulfur oxide emissions.Tostudy the whole competitive process changing with the increase of the loading,the dynamic competition adsorption mechanism of cyclohexene and thiophene in siliceous faujasite(FAU)zeolite was analyzed by the Monte Carlo simulation.The results showed that with the increase of the loading,thiophene and cyclohexene had different performances before and after the inflection point of 40 molecule/UC.The adsorbates were distributed ideally at optimal sites during the stage that occurred before the inflection point,which is called the“optimal-displacement adsorption”stage.When approaching the inflection point,the competition became apparent and the displacement appeared accordingly,some thiophene molecules at S sites(refers to the sites inside the supercages)were displaced by cyclohexene.After the inflection point,the concentration of adsorbates at W sites(refers to the 12-membered ring connecting the supercages)was significantly reduced,whereas the adsorbates at S sites got more concentrated.The stage some cyclohexene molecules displaced by thiophene and inserted into the center of the supercage can be named as the“insertion-displacement adsorption”stage,and both the adsorption behavior and the competitive relationship became localized when the adsorption amount became saturated.This shift in the competitive adsorption mechanism was due to the sharp increase of interaction energy between the adsorbates.Besides,the increase in temperature and ratio of Si/Al will allow the adsorbates,especially thiophene molecules to occupy more adsorption sites,and it is beneficial to improve the desulfurization selectivity.
文摘Atomic force microscopy (AFM) was used to study the competitive adsorption betweenbovine serum albumin (BSA) and type Ⅰ collagen on hydrophilic and hydrophobic silicon wafers.BSA showed a grain shape and the type Ⅰ collagen displayed fibril-like molecules with relativelyhomogeneous height and width, characterized with clear twisting (helical formation). These AFMimages illustrated that quite a lot of type Ⅰ collagen appeared in the adsorption layer on hydrophilicsurface in a competitive adsorption state, but the adsorption of BSA was more preponderant than thatof type Ⅰ collagen on hydrophobic silicon wafer surface. The experiments showed that theinfluence of BSA on type Ⅰ collagen adsorption on hydrophilic surface was less than that onhydrophobic surface.
基金Funded by the National Natural Science Foundation of China(No.51202173)National College Students Innovation and Entrepreneurship Training Program(2015)
文摘Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the fluidity of mortar decreased sharply,so it should be used together with a superplasticizer to enable good workability.With its powerful charge density in the molecular structure,the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process.Consequently,we experimentally studied on the bleeding rate and rheological properties of cement slurry,fluidity and mechanical properties of mortar with welan gum mixed with superplasticizer,aiming at understanding the competitive adsorption phenomenon by application of welan gum mixed with superplasticizer.By measuring the hydration heat and zeta potential,the mechanism of interaction of welan gum with superplasticizer was deduced and explained.The results showed that it could ensure a good dispersion effect when welan gum is mixed with the two kinds of superplasticizer.Welan gum had little impact on the naphthalene superplasticizer,but did have a substantial influence on polycarboxylate.In practice,adding welan gum after PCE acted with cement for 2 min could effectively avoid the competitive adsorption and then achieve better performance.On this viewpoint for mortar with PCE,new delay release welan gum needs further research and development.
基金supported by Major Natural Science Foundation of Guangdong Provincethe Trans-century Training Programmed Foundation for the Talents of the State Education Ministry of Chinaand the Foundation for the Key Teachers in Chinese University
文摘The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures included benzene/toluene, toluene/xylene, benzene/isopropylbenzene, ethyl acetate/toluene and benzene/ethyl acetate. Experimental results show that various ACF-Ps, as with ACF-W, can remove both vapors in binary vapor mixtures with over 99% of removal efficiency before the breakthrough point of the more weakly adsorbed vapor. In dynamic competitive adsorption, the more weakly adsorbed vapor not only penetrates early, but also will be displaced and desorbed consequently by stronger adsorbate and therefore produces a rolling up in the breakthrough curve. The ACF-Ps prepared at different temperatures have somewhat different adsorption selectivity. The feed concentration ratio of vapors, the length/diameter ratio and the thick of bed have effect on competitive adsorption. The competitive adsorption ability of a vapor is mainly related to its boiling point. Usually, the higher the boiling point, the stronger the vapor adsorbed on ACF-P.
基金support from the National Natural Science Foundation of China (22325808,U22B20140,22021004)。
文摘An in-depth understanding of the competition mechanism between olefins and different types of sulfides in gasoline is essential to improve the desulfurization selectivity of the adsorption desulfurization process(ADS).In this study,the competitive adsorption and diffusion mechanism of two systems,diethyl sulfide/cyclohexene and n-butyl mercaptan/cyclohexene,with different adsorption amounts in siliceous faujasite zeolite(FAU) were investigated by Monte Carlo(MC) and molecular dynamics(MD).The systems exhibited a two-stage loading-dependent competitive adsorption and diffusion mechanism,with an inflection point of 32 molecule/UC(moleculers per microcoulomb).Before the inflection point(4-32molecule/UC),the competition mechanism of the two systems was the "optimal-displacement" mechanism.After the inflection point,the mechanism of the diethyl sulfide/cyclohexene changed to "relocation-displacement",while that of the n-butyl mercaptan/cyclohexene system changed to "dominantdisplacement".Compared to ether functional groups,the alcohol functional group has higher polarity and stronger adsorption stability,thus occupying more favorable adsorption sites within the supercages(SCs),while ethyl sulfide shifts outward to other sites within other SCs.In addition,the diffusion performance of adsorbent is related to the adsorption energy.The lower the adsorption energy,the weaker the diffusion ability.Meanwhile,the diffusion performance of adsorbates is better at high temperatures and low adsorption capacity.The effect of temperatu re on the desulfu rization selectivity was determined.A lower temperature is favorable for the adsorption capacity of the two systems and the removal selectivity of sulfides.This study provides fundamental insights into the competitive adsorption and diffusion mechanisms among sulfides,mercaptans and olefins,offering theoretical guidance for adsorbent design and reaction temperature optimization.
基金supported by the National Science Fund for Distinguished Young Scholars(No.51925404)the National Natural Science Foundation of China(Nos.52104233,52104228 and 52404261)the Fundamental Research Funds for the Central Universities(No.2023ZDPY05).
文摘This study mainly investigates the influence of pore water characteristics on the adsorption properties of coalbed methane through integrated low field nuclear magnetic resonance(LF-NMR),adsorption experiments,and molecular dynamics(MD)simulations.Pore water states in three coal ranks were characterized during progressive hydration.Multi-scale analysis revealed how pore water evolution regulates methane adsorption processes.During the diffusion-dominated stage(M2-M3),adsorbed water penetrates into the micropores.In the highly wettable brown coal(L1),the adsorbed water content reaches 2.12 g while in the anthracite(A1),it is only 0.29 g.During the active water injection stage(M4-M6),non-adsorbed water dominates in anthracite(over 85%of the total water content of 4.01 g),while adsorbed water remains dominant in lignite(over 60%of the total water content of 3.52 g).Water content plays a key role in methane adsorption in coal.During the water addition phase,the influence of methane adsorption on medium-to-low-rank coal is relatively weak,while the methane adsorption capacity of high-rank coal A1 shows a significant decrease during both the water diffusion and water addition phases,corresponding to a reduction in Langmuir volume of 21.22 cm^(3)/g.Molecular dynamics(MD)results further show that the free energy between molecules on the surface of hydroxyl-modified coal increases,with hydroxyl groups driving electrostatic interactions between coal and water molecules.Increased steric hindrance inhibits hydrogen bond formation and reduces the rate of hydrogen bond growth.There is a significant correlation between pore water content and coal-water molecular interaction energy,which cross-scale validates the results of LF-NMR testing and MD simulations.
基金financially supported by the National Key Research and Development Program of China(No.2017YFD0800305)。
文摘As the fundamental unit of soil,aggregates exhibit significant variations in their abilities to adsorb and desorb trace elements,depending on their size.Batch experiments were conducted to investigate the characteristics of adsorption and desorption of cadmium(Cd),copper(Cu),and lead(Pb)on and from soil aggregate fractions from three layers of a calcareous soil profile in Changxing County,Zhejiang Prvince,China.The results showed that both Langmuir and Freundlich models successfully described the isothermal adsorption processes of single Cd,Cu,and Pb on different soil aggregates.Additionally,aggregates from the bottom soil layer showed the highest maximum adsorption capacity and required the lowest energy for Cd,Cu,and Pb adsorption compared to aggregates from upper soil layers.The physicochemical properties of soil aggregates were found to govern the adsorption and desorption processes of heavy metals rather than the aggregate size,wherein the contents of iron/aluminum oxides and organic matter were the most crucial influencing factors.Cadmium displayed higher mobility than Cu and Pb in different soil aggregates,and the maximum adsorption capacities of the metal ions followed the order of Pb>Cu>Cd,while their desorption rates followed the order of Cd>Cu>Pb.Additionally,the<0.053 mm microaggregates presented the lowest desorption rates for Cd,Cu,and Pb compared to other soil aggregate fractions in each soil layer.Furthermore,the orthogonal experiment results demonstrated that the competitive adsorption between metals occurred on soil aggregates in the ternary heavy metal system,but only the desorption of Pb was significantly affected by the coexistence of Cd and Cu.
文摘The competitive adsorption and desorption of Pb（II） and Cu（II） ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 tool. L^-1 CaC12 as background electrolyte. The desorption isotherms of Pb（lI） and Cu（II） were similar to the adsorption isotherms, which can be fitted well by Freundlich equation （R2 〉 0.96）. The soil in the three sites had greater sorption capacities for Pb（II） than Cu （II）, which was affected strongly by the soil characteristics. In the binary metal solution containing 1 ： 1 molar ratio of Pb（II） and Cu（II）, the total amount of Pb（II） and Cu（lI） adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared （FT-IR） spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.
基金This work was supported by the National Natural Science Foundation of China(No.41372152)the National Basic Research Program of China(973 Program,2014CB744302).
文摘Shale gas is an unconventional gas source with substantial development potential.In this study,Longmaxi Formation shale from the Silurian system in Yibin,Sichuan Province was collected for characterizing total organic carbon(TOC),clay mineral content,and other reservoir properties.The pore structure of shale was analyzed by field-emission scanning electron microscopy and low-temperature N_(2) adsorption–desorption method.Isothermal adsorption experiments for CH_(4)and CO_(2)mixtures in shale samples were performed.The second Virial coefficient was used to calculate for the compressibility factor of the gas mixture.The influencing factors of gas adsorption capacity of shale were analyzed.Finally,the CH_(4)and CO_(2)adsorption capacities and selection of shale samples were investigated.Under low pressure,the total gas mixture capacity of shale samples was positively correlated with pressure.When the pressure increased to a certain extent,the growth trend of gas mixture adsorption capacity of shale samples decreased.The mixed gas adsorption volume is high at 50℃ for all the proportion.Given the same temperature and pressure,the CO_(2)adsorption of shale samples is higher than the CH_(4)adsorption.In competitive adsorption,shale prefers to adsorb CO_(2).Therefore,CO_(2)is easier to be adsorbed by shale and this causes CH_(4)to be released from the adsorption site.
