Since the capacity of CO2 adsorption of coal is a key factor in coal and CO2 outbursts,an experimental study was carried out on CO2 isothermal adsorption with high-pressure volumetry with dry coal samples from the No....Since the capacity of CO2 adsorption of coal is a key factor in coal and CO2 outbursts,an experimental study was carried out on CO2 isothermal adsorption with high-pressure volumetry with dry coal samples from the No.2 coal seam in the Haishiwan Coalfield.Four different equations(Langmuir,BET,D-R and D-A) were used to fit the experimental data.We discuss adsorption mechanisms.The results show that the amount of CO2 adsorption increases rapidly under low relative pressure,i.e.,the ratio of equilibrium pressure and saturated vapor pressure,which indicates that molecular layer adsorption or micropore filling may occur in coal.No clear equilibrium state was observed on the isothermal adsorption curves under relative pressure(P /P0 ) ranging from 0 to 0.8.The fitted results show that the accuracy of the D-A equation is highest with n=1.Micropores are more developed in coal by comparing the BET equation with a pressure mercury injection method on the surface area.The D-A equation(n=1) provides the best fit.By comparing the calculated specific surface area of the BET equation and the mercury intrusion method,it is found that micropore adsorption of CO2 occupies a dominant position.展开更多
Quantitative description of desorption stages of coalbed methane is an important basis to objectively understand the production of coalbed methane well,to diagnose the production state,and to optimize the management o...Quantitative description of desorption stages of coalbed methane is an important basis to objectively understand the production of coalbed methane well,to diagnose the production state,and to optimize the management of draining and collection of coalbed methane.A series of isothermal adsorption experiments were carried out with 12 anthracite samples from 6 coalbed methane wells located in the south of the Qinshui Basin,based on the results of isothermal adsorption experiments,and an analytical model was developed based on the Langmuir sorption theory.With the model,a numerical method that adopts equivalent desorption rate and its curve was established,which can be used to characterize the staged desorption of coalbed methane.According to the experimental and numerical characterizations,three key pressure points determined by the equivalent desorption rate curvature that defines pressure-declining desorption stage,have been proposed and confirmed,namely,start-up pressure,transition pressure and sensitive pressure.By using these three key pressure points,the process of coalbed methane desorption associated with isothermal adsorption experiments can be divided into four stages,i.e.,zero desorption stage,slow desorption stage,transition desorption stage,and sensitive desorption stage.According to analogy analysis,there are differences and similarities between the processes of coalbed methane desorption identified by isothermal adsorption experiments and observed in gas production.Moreover,it has been found that larger Langmuir volume and ratio of Langmuir constants are beneficial to earlier advent of steady production stage,whereas it is also possible that the declining production stage may occur ahead of schedule.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
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
Ammonium adsorption and desorption properties by purple soils with dif- ferent pH were studied. The results showed that the adsorption and desorption amounts of NH4＋ by purple soils increased with the increase of NH4...Ammonium adsorption and desorption properties by purple soils with dif- ferent pH were studied. The results showed that the adsorption and desorption amounts of NH4＋ by purple soils increased with the increase of NH4＋ concentration, regardless of soil pH values; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 6.0 were 10.3 and 7.96 mg/g, respectively; the largest adsorp- tion and desorption amounts of NH4＋ by purple soil at pH 7.2 were 12.8 and 4.62 mg/g, respectively; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 8.0 were 13.5 and 2.23 mg/g, respectively. The isothermal adsorption ki- netics of NH4＋ by purple soils fits the Freundlich equation best （R〉0.95）. This study shows that the adsorption of NH4＋ by purple soils with different pH values is multi- molecular layer uneven surface adsorption.展开更多
The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects.Firstly,a physical model of adsorption and desorption of methane molecu...The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects.Firstly,a physical model of adsorption and desorption of methane molecules on micropores was established.Secondly,a grand canonical ensemble was introduced as the Monte Carlo simulation system.Thirdly,based on the model and system,the molecule simulation program was developed with VC++6.0 to simulate the isothermal adsorption relationship between the amount of molecule absorption and the factors affecting it.Lastly,the numerically simulated results were compared with measured results of adsorption coal samples of two different coal mines with a laboratory gas absorption instrument.The results show that the molecule simulations of the adsorption constants,the adsorption quantity,and the isothermal adsorption curve at the same and different coal temperatures were in good agreement with those measured in the experiments,indicating that it is feasible to use the established model and the Monte Carlo molecule simulation to study the adsorption characteristics of methane molecules in coal.展开更多
The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillon...The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillonite molecule and[Cu(H_(2)O)_(6)]^(2+)or[Zn(H_(2)O)_(6)]^(2+)was possible.The experimental results of powder X-ray diffraction and isothermal adsorption supported the above-mentioned calculation results.展开更多
The adsorption characteristics of Pb on sediments of the Dianshan Lake in Shanghai was studied. The results show that (1) the relationship between the amount q of apparent equilibrium adsorption and the equilibrium co...The adsorption characteristics of Pb on sediments of the Dianshan Lake in Shanghai was studied. The results show that (1) the relationship between the amount q of apparent equilibrium adsorption and the equilibrium concentration C conforms to the Freundlich isothermal adsorption equation; (2) the adsorption and desorption of Pb on sediments are not reversible, that is, adsorption/desorption of Pb exhibits hysteresis; (3) Pb adsorption behavior is initially fast, followed by a slow reaction, and the slow reaction conforms to a reversible first-order reaction; (4) by deducing the Pb adsorption kinetics, four kinetics parameters n,k 1,k 2,q (max) independent of C could be worked out; (5) the equilibrium parameter (K) and the free energy change (ΔG) could also be determined, and the negative values of free energy change (ΔG) indicate the spontaneous nature of the adsorption.展开更多
In order to improve the calculation method of the isosteric adsorption heat,clarify thermodynamic characteristics of CH4 adsorption by continental shale and reveal the adsorption mechanism,this paper selected shale sa...In order to improve the calculation method of the isosteric adsorption heat,clarify thermodynamic characteristics of CH4 adsorption by continental shale and reveal the adsorption mechanism,this paper selected shale samples from the seventh Member of Yanchang Formation of Upper Triassic in the Yanchang Gasfield of the Ordos Basin as the research object.The isothermal adsorption experiment was carried out on the CH4 adsorption by continental shale and the excess adsorption curves were plotted.Then,the characteristics of the isosteric adsorption heat of the shale with different types of adsorption capacity were illustrated by analyzing and comparing the difference between excess and absolute adsorption capacity.And the following research results were obtained.First,under the same temperature and pressure,absolute adsorption capacity is higher than the excess values.The difference between them is higher under low temperature and high pressure and it is in the relationship of exponential function with the equilibrium pressure.If excess adsorption capacity is used to evaluate the adsorptive property of shale reservoirs,the evaluation result will be underestimated.Second,for CH4 adsorption by Yanchang Formation shale,the absolute and excess isosteric adsorption heat values have a linear positive correlation with absolute and excess adsorption capacity respectively,and the intermo-lecular force of adsorbate has a dominant effect on isosteric adsorption heat values.Third,absolute isosteric adsorption heat value is less than the excess heat.The relative error is in the range of 18.18e49.79%,and it is higher in the stage with low adsorption capacity.If excess adsorption capacity is taken as the basic data to calculate initial isosteric adsorption heat values,the calculation result will be overvalued,and consequently,the evaluation of the intermolecular force of adsorbent and adsorbate is overestimated.展开更多
In the calculation of shale gas resources/reserves,isothermal adsorption parameters are mainly determined by dry sample data at the laboratory temperature,and the regression effect of total organic carbon content(TOC)...In the calculation of shale gas resources/reserves,isothermal adsorption parameters are mainly determined by dry sample data at the laboratory temperature,and the regression effect of total organic carbon content(TOC)isothermal adsorption parameters is poor.Based on the physical significance of key parameters in Langmuir and Henry adsorption models,the problems in determining the isothermal adsorption parameters in the calculation of shale gas reserves/reserves are analyzed by taking the marine shale in the Upper Ordovician Wufeng FormingeLower Silurian Longmaxi Formation in the Sichuan Basin as an example.Based on a large number of measured isothermal adsorption data,the effects of TOC,temperature and water saturation on the shale gas adsorption parameters are analyzed.The influence model of TOC,temperature and water saturation on isothermal adsorption parameters of shale gas is established,and a novel method for calculating the adsorption parameters of shale gas from under experimental conditions to original reservoir conditions is proposed.The results are obtained as follows.First,there are problems in the calculation of shale gas resources/reserves,such as poor and contradictoryfitting relation between isothermal adsorption parameters and TOC,difficulty in the conversion of Van't Hoff equation,and difficulty in direct application of water saturation(Sw)in resource/reserves calculation.Second,the problem of poor directfitting relation between Langmuir pressure(pL)and TOC is solved by integrating the Langmuir adsorption model with the Henry adsorption model and by establishing a new parameter e Henry constant a for methane adsorption capacity of shale.Third,when Sw<40%,the Langmuir volume(VL)is linearly negatively correlated with Sw;when Sw<20%,a is constant relatively;by establishing the relationship between the normalized absolute adsorption capacity and Sw(<50%)under the pressure exceeding 30 MPa,the effect of Sw on the isothermal adsorption capacity can be calculated.Fourth,the in-situ stress in the Wufeng FormationeLongmaxi Formation shale reservoir affects the adsorption capacity of shale.For shale reservoirs with the same TOC,the higher the in-situ stress,the smaller the VL and a values.Under high pressure(>30 MPa),the effect of Sw on the methane adsorption capacity of shale shows a similar trend,and the effect of water molecules on the adsorption capacity on shale pore surface is constant.It is concluded that the proposed novel method for determining the isothermal adsorption parameters of shale with different TOC,temperature and water saturation conditions provides a technical support for the accurate calculation of shale gas resources/reserves and contributes to the scientific development of shale gas industry.展开更多
A series of chitosan-g-poly （acrylic acid）/vermiculite hydrogel composites were synthesized and used as adsorbents for the investigation of the effect of process parameters such as vermiculite content, pH of dye sol...A series of chitosan-g-poly （acrylic acid）/vermiculite hydrogel composites were synthesized and used as adsorbents for the investigation of the effect of process parameters such as vermiculite content, pH of dye solution, contact time, initial concentration of dye solution, temperature, ionic strength and concentration of surfactant sodium dodecyl sulfate on the removal of Methylene Blue （MB） from aqueous solution. The results showed that the adsorption capacity for dye increased with increasing pH, contact time and initial dye concentration, but decreased with increasing temperature, ionic strength and sodium dodecyl sulfate concentration in the present of the surfactant. The adsorption kinetics of MB onto the hydrogel composite followed pseudo second-order kinetics and the adsorption equilibrium data obeyed Langmuir isotherm. By introducing 10 wt.% vermiculite into chitosan-g-poly （acrylic acid） polymeric network, the obtaining hydrogel composite showed the highest adsorption capacity for MB, and then could be regarded as a potential adsorbent for cationic dye removal in a wastewater treatment process.展开更多
Batch adsorption from aqueous solutions in a slightly basic medium of Methylene Blue, up to 2500 mg/L, onto synthetic magnesium silicate （Florisil） of three particle size ranges （mean diameters of 112, 200 and 425 ...Batch adsorption from aqueous solutions in a slightly basic medium of Methylene Blue, up to 2500 mg/L, onto synthetic magnesium silicate （Florisil） of three particle size ranges （mean diameters of 112, 200 and 425 μm） was compared to the corresponding adsorption onto activated carbon and Amberlite XAD-2. The best fit of the kinetic results was achieved by a pseudo second-order equation. The equilibrium data were found to be well represented by the Langmuir isotherm equation. Amberlite XAD-2, an unspecific adsorbent capable of adsorbing exclusively through a surface effect, exhibited a poor dye uptake, confirming that the adsorption mechanism on Florisil was due to electrostatic attraction and ion exchange. Moreover, the comparison between Florisil and the other adsorbents was performed on the basis of the evaluation of the surface area and pore volume occupied by the adsorbed dye.展开更多
Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate...Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char （APTC） for Rhodamine B （RhB）. Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little effect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.展开更多
Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibriu...Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was deter...展开更多
The adsorption of phosphate onto ferrihydrite(FH) and two FH-humic acid(HA) complexes, obtained by co-precipitating FH with low(FH-HA1) and relatively high amounts of humic acid(FH-HA2), was studied through kinetics a...The adsorption of phosphate onto ferrihydrite(FH) and two FH-humic acid(HA) complexes, obtained by co-precipitating FH with low(FH-HA1) and relatively high amounts of humic acid(FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanisms of phosphate adsorption onto two soil compositions. The isoelectric point(IEP) and the specific surface area(SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower p H, and the increase in the ionic strength promoted phosphate adsorption at a higher p H.However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower p H and increased the adsorption at a higher pH.展开更多
The adsorption potential of titanium dioxide （TiO2） nanoparticles for removing arsenic from drinking water was evaluated. Pure and iron-doped TiO2 particles are synthesized via sol-gel method. The synthesized TiO2 n...The adsorption potential of titanium dioxide （TiO2） nanoparticles for removing arsenic from drinking water was evaluated. Pure and iron-doped TiO2 particles are synthesized via sol-gel method. The synthesized TiO2 nanoparticles were then immobilized on ordinary sand for adsorption studies. Adsorption isotherms were conducted on the synthesized nanoparticles as well as the sand coated with TiO2 nanoparticles under varying conditions of air and light, namely, the air-sunlight （A-SL）, air-light （AL）, air-dark （AD） and nitrogen-dark （ND）. X-ray diffraction （XRD） analysis showed that the pure and iron-doped TiO2 nanoparticles were in 100% anatase crystalline phase with crystai sizes of 108 and 65 nm, respectively. Adsorption of arsenic on the three adsorbents was non-linear that could be described by the Freundlich and Langmuir adsorption models. Iron doping enhanced the adsorption capacity of TiO2 nanoparticles by arresting the grain growth and making it visible light responsive resulting in a higher affinity for arsenic. Similarly, the arsenic removal by adsorption on the sand coated with TiO2 nanoparticles was the highest among the three types of sand used. In all cases, As（V） was adsorbed more compared with As（Ⅲ）. The solution pH appeared to be the most important factor in controlling the amount of arsenic adsorbed.展开更多
Removal of lead and cadmium ions from aqueous solutions by adsorption process was investigated. Low cost and locally available natural mineral of manganoxide mineral was used as an adsorbent. The kinetics of adsorptio...Removal of lead and cadmium ions from aqueous solutions by adsorption process was investigated. Low cost and locally available natural mineral of manganoxide mineral was used as an adsorbent. The kinetics of adsorption process data was examined using the pseudo-first-order, pseudo-second-order kinetics and the intra-particle diffusion models. The rate constants of adsorption for all these kinetics models were calculated and compared. The adsorption kinetics was best described by the pseudo second-order model. The Langmuir and Freundlich adsorption isotherm models were applied to the experimental equilibrium data at different temperatures. The experimental data well fitted to Langmuir isotherm model. The maximum adsorption capacities of manganoxide mineral for lead and cadmium ions were calculated from the Langmuir isotherm and were 98 and 6.8 mg/g, respectively. Thermodynamic parameters such as the change of Gibbs free energy, enthalpy and entropy of adsorption were also calculated and it was found that the lead and cadmium uptake reactions by manganoxide mineral were endothermic and spontaneous in nature. Therefore, manganoxide mineral can be used as adsorbents for lead and cadmium ions removal processes as an alternative natural mineral among the others.展开更多
The adsorption of dibenzofuran on three commercial granular activated carbons (ACs) was investigated by dynamic experiment to correlate the adsorption equilibrium and kinetics with the structure of activated carbons.P...The adsorption of dibenzofuran on three commercial granular activated carbons (ACs) was investigated by dynamic experiment to correlate the adsorption equilibrium and kinetics with the structure of activated carbons.Physical properties including surface area, average pore diameter, micropore area and micropore volume of the activated carbons were characterized by N2 adsorption experiment on ASAP2010. To calculate the adsorption parameters, adsorption isotherm data were fitted to the Langmuir equation, and adsorption kinetic data were fitted to the linear driving force (LDF) diffusion model. From the correlation results, it is concluded that the adsorption equilibrium and diffusion coefficient of dibenzofuran on activated carbon are controlled respectively by the total adsorbent surface area and the adsorbent pore diameter.展开更多
Azo dyes have received considerable attention because of their association with various human health problems. The aim of the investigation is to determine the adsorption behavior ofazo dyes in aqueous solution on DG0...Azo dyes have received considerable attention because of their association with various human health problems. The aim of the investigation is to determine the adsorption behavior ofazo dyes in aqueous solution on DG06, GSE17200, and GSE17201 soils using C. I. Acid Red 14 （AR14） as example. The experimental results indicate that the Freundlich model expresses the adsorption isotherm better than the Langmuir model and the pseudo-second-order model achieves adsorption of AR14 on the three soils well. Based on the pseudo-second-order model, the adsorption thermodynamic of AR14 on DG06 soil have been studied and the thermodynamics parameter of AGO is determined and AGO value shows the adsorption process of AR14 on DG06 is mainly physical in nature. Furthermore, the effects of temperature, pH and salinity （NaC1） on adsorption have been investigated. The decrease in pH or the increase in salinity enhances the adsorption of AR14 by DG06, GSE17200, and GSE17201.展开更多
The potential of di-(m-Formylphenol)-1,2-cyclohexandiimine as an environmentally friendly corrosion inhibitor for steel was investigated in 1 mol/L HCl using potentiodynamic polarization, electrochemical impedance spe...The potential of di-(m-Formylphenol)-1,2-cyclohexandiimine as an environmentally friendly corrosion inhibitor for steel was investigated in 1 mol/L HCl using potentiodynamic polarization, electrochemical impedance spectroscopy and chronoamperometry measurements. All electrochemical measurements suggest that this compound is an excellent corrosion inhibitor for mild steel and the inhibition efficiency increases with the increase in inhibitor concentration. The effect of temperature on the corrosion behavior of mild steel with the addition of the Schiff base was studied in the temperature range from 25 °C to 65 °C. It is found that the adsorption of this inhibitor follows the Langmuir adsorption isotherms. The value of activation energy and the thermodynamic parameters such as ΔHads, ΔSads, Kads and ΔGads were calculated by the corrosion currents at different temperatures using the adsorption isotherm. The morphology of mild steel surface in the absence and presence of inhibitor was examined by scanning electron microscopy(SEM) images.展开更多
基金the National Basic Research Program of China (No.2005CB221503)the Major Program of the National Natural Science Foundation (Nos.70533050 and 50674089) for their support of this project
文摘Since the capacity of CO2 adsorption of coal is a key factor in coal and CO2 outbursts,an experimental study was carried out on CO2 isothermal adsorption with high-pressure volumetry with dry coal samples from the No.2 coal seam in the Haishiwan Coalfield.Four different equations(Langmuir,BET,D-R and D-A) were used to fit the experimental data.We discuss adsorption mechanisms.The results show that the amount of CO2 adsorption increases rapidly under low relative pressure,i.e.,the ratio of equilibrium pressure and saturated vapor pressure,which indicates that molecular layer adsorption or micropore filling may occur in coal.No clear equilibrium state was observed on the isothermal adsorption curves under relative pressure(P /P0 ) ranging from 0 to 0.8.The fitted results show that the accuracy of the D-A equation is highest with n=1.Micropores are more developed in coal by comparing the BET equation with a pressure mercury injection method on the surface area.The D-A equation(n=1) provides the best fit.By comparing the calculated specific surface area of the BET equation and the mercury intrusion method,it is found that micropore adsorption of CO2 occupies a dominant position.
基金supported by National KeyBasic Research Program of China (Grant No. 2009CB219605)Key Project of National Natural Science Foundation of China (Grant No.40730422)Grand Science and Technology Special Project of China(Grant No. 2011ZX05034-04)
文摘Quantitative description of desorption stages of coalbed methane is an important basis to objectively understand the production of coalbed methane well,to diagnose the production state,and to optimize the management of draining and collection of coalbed methane.A series of isothermal adsorption experiments were carried out with 12 anthracite samples from 6 coalbed methane wells located in the south of the Qinshui Basin,based on the results of isothermal adsorption experiments,and an analytical model was developed based on the Langmuir sorption theory.With the model,a numerical method that adopts equivalent desorption rate and its curve was established,which can be used to characterize the staged desorption of coalbed methane.According to the experimental and numerical characterizations,three key pressure points determined by the equivalent desorption rate curvature that defines pressure-declining desorption stage,have been proposed and confirmed,namely,start-up pressure,transition pressure and sensitive pressure.By using these three key pressure points,the process of coalbed methane desorption associated with isothermal adsorption experiments can be divided into four stages,i.e.,zero desorption stage,slow desorption stage,transition desorption stage,and sensitive desorption stage.According to analogy analysis,there are differences and similarities between the processes of coalbed methane desorption identified by isothermal adsorption experiments and observed in gas production.Moreover,it has been found that larger Langmuir volume and ratio of Langmuir constants are beneficial to earlier advent of steady production stage,whereas it is also possible that the declining production stage may occur ahead of schedule.
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.
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Supported by National Natural Science Foundation of China(41271267)National Key Technology Research and Development Program(2013BAJ11B03)Special Scientific Research Fund of Environment Friendly Public Welfare Profession of China(2013467036)~~
文摘Ammonium adsorption and desorption properties by purple soils with dif- ferent pH were studied. The results showed that the adsorption and desorption amounts of NH4＋ by purple soils increased with the increase of NH4＋ concentration, regardless of soil pH values; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 6.0 were 10.3 and 7.96 mg/g, respectively; the largest adsorp- tion and desorption amounts of NH4＋ by purple soil at pH 7.2 were 12.8 and 4.62 mg/g, respectively; the largest adsorption and desorption amounts of NH4＋ by purple soil at pH 8.0 were 13.5 and 2.23 mg/g, respectively. The isothermal adsorption ki- netics of NH4＋ by purple soils fits the Freundlich equation best （R〉0.95）. This study shows that the adsorption of NH4＋ by purple soils with different pH values is multi- molecular layer uneven surface adsorption.
基金supported by the Industrial Research Project in Guizhou Science and Technology Bureau of China (GY(2011)No.3012)International Cooperation Projects in Guizhou Science and Technology Bureau of China (G(2009)No.700111)
文摘The paper presents a Monte Carlo simulation to study the adsorption characteristics of methane molecule on coal slit pores from different aspects.Firstly,a physical model of adsorption and desorption of methane molecules on micropores was established.Secondly,a grand canonical ensemble was introduced as the Monte Carlo simulation system.Thirdly,based on the model and system,the molecule simulation program was developed with VC++6.0 to simulate the isothermal adsorption relationship between the amount of molecule absorption and the factors affecting it.Lastly,the numerically simulated results were compared with measured results of adsorption coal samples of two different coal mines with a laboratory gas absorption instrument.The results show that the molecule simulations of the adsorption constants,the adsorption quantity,and the isothermal adsorption curve at the same and different coal temperatures were in good agreement with those measured in the experiments,indicating that it is feasible to use the established model and the Monte Carlo molecule simulation to study the adsorption characteristics of methane molecules in coal.
文摘The frontier orbital energies of montmorillonite molecule and[Me(H_(2)O)_(6)]^(2+)(Me=Cu^(2+),Zn^(2+),Co^(2+)and Ni^(2+))were calculated by INDO method.Results showed that the chemical interaction between montmorillonite molecule and[Cu(H_(2)O)_(6)]^(2+)or[Zn(H_(2)O)_(6)]^(2+)was possible.The experimental results of powder X-ray diffraction and isothermal adsorption supported the above-mentioned calculation results.
文摘The adsorption characteristics of Pb on sediments of the Dianshan Lake in Shanghai was studied. The results show that (1) the relationship between the amount q of apparent equilibrium adsorption and the equilibrium concentration C conforms to the Freundlich isothermal adsorption equation; (2) the adsorption and desorption of Pb on sediments are not reversible, that is, adsorption/desorption of Pb exhibits hysteresis; (3) Pb adsorption behavior is initially fast, followed by a slow reaction, and the slow reaction conforms to a reversible first-order reaction; (4) by deducing the Pb adsorption kinetics, four kinetics parameters n,k 1,k 2,q (max) independent of C could be worked out; (5) the equilibrium parameter (K) and the free energy change (ΔG) could also be determined, and the negative values of free energy change (ΔG) indicate the spontaneous nature of the adsorption.
基金supported by the National Major Science and Technology Project"Key Technologies for Exploration and Development of Continental Shale Gas in Yan'an"(No.2017ZX05039001005).
文摘In order to improve the calculation method of the isosteric adsorption heat,clarify thermodynamic characteristics of CH4 adsorption by continental shale and reveal the adsorption mechanism,this paper selected shale samples from the seventh Member of Yanchang Formation of Upper Triassic in the Yanchang Gasfield of the Ordos Basin as the research object.The isothermal adsorption experiment was carried out on the CH4 adsorption by continental shale and the excess adsorption curves were plotted.Then,the characteristics of the isosteric adsorption heat of the shale with different types of adsorption capacity were illustrated by analyzing and comparing the difference between excess and absolute adsorption capacity.And the following research results were obtained.First,under the same temperature and pressure,absolute adsorption capacity is higher than the excess values.The difference between them is higher under low temperature and high pressure and it is in the relationship of exponential function with the equilibrium pressure.If excess adsorption capacity is used to evaluate the adsorptive property of shale reservoirs,the evaluation result will be underestimated.Second,for CH4 adsorption by Yanchang Formation shale,the absolute and excess isosteric adsorption heat values have a linear positive correlation with absolute and excess adsorption capacity respectively,and the intermo-lecular force of adsorbate has a dominant effect on isosteric adsorption heat values.Third,absolute isosteric adsorption heat value is less than the excess heat.The relative error is in the range of 18.18e49.79%,and it is higher in the stage with low adsorption capacity.If excess adsorption capacity is taken as the basic data to calculate initial isosteric adsorption heat values,the calculation result will be overvalued,and consequently,the evaluation of the intermolecular force of adsorbent and adsorbate is overestimated.
基金supported by the Scientific Research and Technol-ogy Development Project of PetroChina Company Limited,"Research on Geological Activity Evaluation Technology of shale gas Development Zone"(No.2022DJ80)"Research on Exploration and Development Technology of Marine shale gas"(No.2021DJ19).
文摘In the calculation of shale gas resources/reserves,isothermal adsorption parameters are mainly determined by dry sample data at the laboratory temperature,and the regression effect of total organic carbon content(TOC)isothermal adsorption parameters is poor.Based on the physical significance of key parameters in Langmuir and Henry adsorption models,the problems in determining the isothermal adsorption parameters in the calculation of shale gas reserves/reserves are analyzed by taking the marine shale in the Upper Ordovician Wufeng FormingeLower Silurian Longmaxi Formation in the Sichuan Basin as an example.Based on a large number of measured isothermal adsorption data,the effects of TOC,temperature and water saturation on the shale gas adsorption parameters are analyzed.The influence model of TOC,temperature and water saturation on isothermal adsorption parameters of shale gas is established,and a novel method for calculating the adsorption parameters of shale gas from under experimental conditions to original reservoir conditions is proposed.The results are obtained as follows.First,there are problems in the calculation of shale gas resources/reserves,such as poor and contradictoryfitting relation between isothermal adsorption parameters and TOC,difficulty in the conversion of Van't Hoff equation,and difficulty in direct application of water saturation(Sw)in resource/reserves calculation.Second,the problem of poor directfitting relation between Langmuir pressure(pL)and TOC is solved by integrating the Langmuir adsorption model with the Henry adsorption model and by establishing a new parameter e Henry constant a for methane adsorption capacity of shale.Third,when Sw<40%,the Langmuir volume(VL)is linearly negatively correlated with Sw;when Sw<20%,a is constant relatively;by establishing the relationship between the normalized absolute adsorption capacity and Sw(<50%)under the pressure exceeding 30 MPa,the effect of Sw on the isothermal adsorption capacity can be calculated.Fourth,the in-situ stress in the Wufeng FormationeLongmaxi Formation shale reservoir affects the adsorption capacity of shale.For shale reservoirs with the same TOC,the higher the in-situ stress,the smaller the VL and a values.Under high pressure(>30 MPa),the effect of Sw on the methane adsorption capacity of shale shows a similar trend,and the effect of water molecules on the adsorption capacity on shale pore surface is constant.It is concluded that the proposed novel method for determining the isothermal adsorption parameters of shale with different TOC,temperature and water saturation conditions provides a technical support for the accurate calculation of shale gas resources/reserves and contributes to the scientific development of shale gas industry.
基金supported by the National Natural Science Foundation of China (No.20877077)the Project of Jiangsu Provincial Science and Technology Office (No.BE2008087)
文摘A series of chitosan-g-poly （acrylic acid）/vermiculite hydrogel composites were synthesized and used as adsorbents for the investigation of the effect of process parameters such as vermiculite content, pH of dye solution, contact time, initial concentration of dye solution, temperature, ionic strength and concentration of surfactant sodium dodecyl sulfate on the removal of Methylene Blue （MB） from aqueous solution. The results showed that the adsorption capacity for dye increased with increasing pH, contact time and initial dye concentration, but decreased with increasing temperature, ionic strength and sodium dodecyl sulfate concentration in the present of the surfactant. The adsorption kinetics of MB onto the hydrogel composite followed pseudo second-order kinetics and the adsorption equilibrium data obeyed Langmuir isotherm. By introducing 10 wt.% vermiculite into chitosan-g-poly （acrylic acid） polymeric network, the obtaining hydrogel composite showed the highest adsorption capacity for MB, and then could be regarded as a potential adsorbent for cationic dye removal in a wastewater treatment process.
文摘Batch adsorption from aqueous solutions in a slightly basic medium of Methylene Blue, up to 2500 mg/L, onto synthetic magnesium silicate （Florisil） of three particle size ranges （mean diameters of 112, 200 and 425 μm） was compared to the corresponding adsorption onto activated carbon and Amberlite XAD-2. The best fit of the kinetic results was achieved by a pseudo second-order equation. The equilibrium data were found to be well represented by the Langmuir isotherm equation. Amberlite XAD-2, an unspecific adsorbent capable of adsorbing exclusively through a surface effect, exhibited a poor dye uptake, confirming that the adsorption mechanism on Florisil was due to electrostatic attraction and ion exchange. Moreover, the comparison between Florisil and the other adsorbents was performed on the basis of the evaluation of the surface area and pore volume occupied by the adsorbed dye.
基金supported by the National Key Technologies R & D Program of China (No. 2006BAC02A12)the Key Technologies R & D Program of Tianjin, China (No.07ZCGYSH02000)the Natural Science Foundationof Tianjin, China (No. 08JCZDJC21400).
文摘Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char （APTC） for Rhodamine B （RhB）. Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little effect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle diffusion model with more than one process affecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.
基金the China PostdoctoralScience Foundation (No. 20070420811)the Edu-cation Department of Henan Province in China (No.200510459016)
文摘Adsorption of Neutral Red (NR) onto peanut husk in aqueous solutions was investigated at 295 K. Experiments were carried out as function of pH, adsorbent dosage, contact time, and initial concentration. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Temkin, Dubinin-Radushkevich, and Toth isotherm models. The results indicated that the Toth and Langmuir models provided the best correlation of the experimental data. The adsorption capacity of peanut husk for the removal of NR was deter...
基金supported by the National Natural Science Foundation of China (Nos. 41071165 and 30890130)
文摘The adsorption of phosphate onto ferrihydrite(FH) and two FH-humic acid(HA) complexes, obtained by co-precipitating FH with low(FH-HA1) and relatively high amounts of humic acid(FH-HA2), was studied through kinetics and isotherm experiments to determine the differences in phosphate adsorption between FH-HA complexes and FH and to reveal the mechanisms of phosphate adsorption onto two soil compositions. The isoelectric point(IEP) and the specific surface area(SSA) of the mineral decreased as the particle porosity of the mineral increased, which corresponded to an increase in the amount of organic carbon. The adsorption capacity of phosphate was higher on FH than on FH-HA1 and FH-HA2 at the scale of micromoles per kilogram. The initial adsorption rate and adsorption affinity of phosphate decreased with an increase in the amount of HA in the mineral. The sensitivity of phosphate adsorption to the change in the pH was greater for FH than for FH-HA complexes. Ionic strength did not affect the adsorption of phosphate onto FH and FH-HA1 at a lower p H, and the increase in the ionic strength promoted phosphate adsorption at a higher p H.However, for the FH-HA2 complex, the increase in the ionic strength inhibited the adsorption of phosphate onto FH-HA2 at a lower p H and increased the adsorption at a higher pH.
文摘The adsorption potential of titanium dioxide （TiO2） nanoparticles for removing arsenic from drinking water was evaluated. Pure and iron-doped TiO2 particles are synthesized via sol-gel method. The synthesized TiO2 nanoparticles were then immobilized on ordinary sand for adsorption studies. Adsorption isotherms were conducted on the synthesized nanoparticles as well as the sand coated with TiO2 nanoparticles under varying conditions of air and light, namely, the air-sunlight （A-SL）, air-light （AL）, air-dark （AD） and nitrogen-dark （ND）. X-ray diffraction （XRD） analysis showed that the pure and iron-doped TiO2 nanoparticles were in 100% anatase crystalline phase with crystai sizes of 108 and 65 nm, respectively. Adsorption of arsenic on the three adsorbents was non-linear that could be described by the Freundlich and Langmuir adsorption models. Iron doping enhanced the adsorption capacity of TiO2 nanoparticles by arresting the grain growth and making it visible light responsive resulting in a higher affinity for arsenic. Similarly, the arsenic removal by adsorption on the sand coated with TiO2 nanoparticles was the highest among the three types of sand used. In all cases, As（V） was adsorbed more compared with As（Ⅲ）. The solution pH appeared to be the most important factor in controlling the amount of arsenic adsorbed.
文摘Removal of lead and cadmium ions from aqueous solutions by adsorption process was investigated. Low cost and locally available natural mineral of manganoxide mineral was used as an adsorbent. The kinetics of adsorption process data was examined using the pseudo-first-order, pseudo-second-order kinetics and the intra-particle diffusion models. The rate constants of adsorption for all these kinetics models were calculated and compared. The adsorption kinetics was best described by the pseudo second-order model. The Langmuir and Freundlich adsorption isotherm models were applied to the experimental equilibrium data at different temperatures. The experimental data well fitted to Langmuir isotherm model. The maximum adsorption capacities of manganoxide mineral for lead and cadmium ions were calculated from the Langmuir isotherm and were 98 and 6.8 mg/g, respectively. Thermodynamic parameters such as the change of Gibbs free energy, enthalpy and entropy of adsorption were also calculated and it was found that the lead and cadmium uptake reactions by manganoxide mineral were endothermic and spontaneous in nature. Therefore, manganoxide mineral can be used as adsorbents for lead and cadmium ions removal processes as an alternative natural mineral among the others.
文摘The adsorption of dibenzofuran on three commercial granular activated carbons (ACs) was investigated by dynamic experiment to correlate the adsorption equilibrium and kinetics with the structure of activated carbons.Physical properties including surface area, average pore diameter, micropore area and micropore volume of the activated carbons were characterized by N2 adsorption experiment on ASAP2010. To calculate the adsorption parameters, adsorption isotherm data were fitted to the Langmuir equation, and adsorption kinetic data were fitted to the linear driving force (LDF) diffusion model. From the correlation results, it is concluded that the adsorption equilibrium and diffusion coefficient of dibenzofuran on activated carbon are controlled respectively by the total adsorbent surface area and the adsorbent pore diameter.
文摘Azo dyes have received considerable attention because of their association with various human health problems. The aim of the investigation is to determine the adsorption behavior ofazo dyes in aqueous solution on DG06, GSE17200, and GSE17201 soils using C. I. Acid Red 14 （AR14） as example. The experimental results indicate that the Freundlich model expresses the adsorption isotherm better than the Langmuir model and the pseudo-second-order model achieves adsorption of AR14 on the three soils well. Based on the pseudo-second-order model, the adsorption thermodynamic of AR14 on DG06 soil have been studied and the thermodynamics parameter of AGO is determined and AGO value shows the adsorption process of AR14 on DG06 is mainly physical in nature. Furthermore, the effects of temperature, pH and salinity （NaC1） on adsorption have been investigated. The decrease in pH or the increase in salinity enhances the adsorption of AR14 by DG06, GSE17200, and GSE17201.
文摘The potential of di-(m-Formylphenol)-1,2-cyclohexandiimine as an environmentally friendly corrosion inhibitor for steel was investigated in 1 mol/L HCl using potentiodynamic polarization, electrochemical impedance spectroscopy and chronoamperometry measurements. All electrochemical measurements suggest that this compound is an excellent corrosion inhibitor for mild steel and the inhibition efficiency increases with the increase in inhibitor concentration. The effect of temperature on the corrosion behavior of mild steel with the addition of the Schiff base was studied in the temperature range from 25 °C to 65 °C. It is found that the adsorption of this inhibitor follows the Langmuir adsorption isotherms. The value of activation energy and the thermodynamic parameters such as ΔHads, ΔSads, Kads and ΔGads were calculated by the corrosion currents at different temperatures using the adsorption isotherm. The morphology of mild steel surface in the absence and presence of inhibitor was examined by scanning electron microscopy(SEM) images.
