Investigations of methane adsorption characteristics on marine-continental transitional shales and gas storage capacity models considering pore evolution

Methane adsorption is a critical assessment of the gas storage capacity(GSC)of shales with geological conditions.Although the related research of marine shales has been well-illustrated,the methane adsorption of marine-continental transitional(MCT)shales is still ambiguous.In this study,a method of combining experimental data with analytical models was used to investigate the methane adsorption characteristics and GSC of MCT shales collected from the Qinshui Basin,China.The Ono-Kondo model was used to fit the adsorption data to obtain the adsorption parameters.Subsequently,the geological model of GSC based on pore evolution was constructed using a representative shale sample with a total organic carbon(TOC)content of 1.71%,and the effects of reservoir pressure coefficient and water saturation on GSC were explored.In experimental results,compared to the composition of the MCT shale,the pore structure dominates the methane adsorption,and meanwhile,the maturity mainly governs the pore structure.Besides,maturity in the middle-eastern region of the Qinshui Basin shows a strong positive correlation with burial depth.The two parameters,micropore pore volume and non-micropore surface area,induce a good fit for the adsorption capacity data of the shale.In simulation results,the depth,pressure coefficient,and water saturation of the shale all affect the GSC.It demonstrates a promising shale gas potential of the MCT shale in a deeper block,especially with low water saturation.Specifically,the economic feasibility of shale gas could be a major consideration for the shale with a depth of<800 m and/or water saturation>60%in the Yushe-Wuxiang area.This study provides a valuable reference for the reservoir evaluation and favorable block search of MCT shale gas.

Thermodynamics and kinetics of adsorption for heavy metal ions from aqueous solutions onto surface amino-bacterial cellulose

Amino-bacterial cellulose（amino-BC） was prepared by chemical modification of bacterial cellulose（BC）.The adsorption characteristics and mechanism of amino-BC were studied.The results show that adsorption data can be fitted well by Langmuir equation and the pseudo-second order kinetics,indicating that the adsorption of amino-BC would obey monolayer molecule adsorption and the main action was chemisorption.Meanwhile,the adsorption process was studied by the Elovich equation and the intra-particle diffusion model,indicating that the absorption characteristics of metal ions on amino-BC is controlled by both film diffusion and particle diffusion.The increase of reaction temperature will accelerate the adsorbing rate because of endothermic reaction.

Adsorption-desorption Characteristics and Thermodynamics of Quinclorac on Minerals

Adsorption-desorption characteristics of quinclorac on montmorillonite, attapulgite and goethite were investigated by the batch equilibrium techniques. The sorption mechanisms of minerals were discussed based on sorption thermodynamics. The results showed that the adsorption of quinclorac on the 3 minerals was included in both rapid stage and slow equilibrium stage. The adsorption kinetics consisted with the pseudo-second-order equation, the particle diffusion equation, and elovich equations, and among them, fitting from the pseudo-second-order was the best. In addition, it could be seen from the nonzero constant C in the particle diffusion equation that the rate of particle diffusion was not a sole factor. The isotherm adsorption-desorption of quinclorac on the 3 clay minerals all fitted Linear and Freundlich equation very well. The adsorption capacities of minerals for quinclorac followed the order of goethite〉montmorillonite〉attapulgite, The desorption of quinclorac presented obvious hysteresis phenomenon on minerals. The study on thermodynamic behavior indicated that the sorption processes of quinclorec onto minerals were spontaneous, and the sorption spontaneity was strengthened with the temperature increasing.

THERMODYNAMICS ADSORPTION OF MANGANESE ION ON 1-(2-PYRIDYLAZO)-2-NAPHTHOL-6-SULPHONIC ACID IMPREGNATED RESIN

An ion-exchange resin of type 201×7 was impregnated with the reagent 1-(2-Pyridylazo)-2-naphthol-6-sulphonic Acid (PAN-S). The adsorption characteristics of PAN-S resin for manganese ion were studied on the static equilibrium adsorption. Within temperature range of 288K^313K and the concentration range investigated, equilibrium data for the adsorption of manganese ions from aqueous solutions by PAN-S resin were obtained and correlated with Freundlich and Langmuir equation. The results showed that the process of the adsorption of manganese ions from aqueous solution by PAN-S was an exothermic process. Estimations of the isothermic enthalpy change of adsorption,free energy change and entropy of adsorption are reported,and the adsorption behaviors are reasonably interpreted.

Study on Adsorption Behavior of P-nitroaniline from Aqueous Solution by Amphiphilic Hollow Carbonaceous Microspheres

[Objective] The research was aimed to study the adsorption behavior of p-nitroaniline from aqueous solution by porous hollow carbonaceous spheres （PHCSs）.[Method] The effects of pH,temperature and amount of carbonaceous microspheres on adsorption behavior of p-nitroaniline were investigated.[Result] The adsorption amount was affected by temperature slightly,and it decreased with the increase of temperature within a certain range.PHCSs had a higher adsorption capacity as pH was in the range of 2.0-8.0.The adsorption amount of p-nitroaniline was proportional to PHCSs amount within a certain range until it reached a saturation level.The adsorption isotherms of p-nitroaniline appeared to be nonlinear and obeyed to Freundlich equation very well.[Conclusion] The amphiphilic property and the specific chemical functional groups of PHCSs enable them to be a potentially excellent sorbent.

Adsorption behavior of Azo Dye C. I. Acid Red 14 in aqueous solution on surface soils

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.

THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS

The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy, and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.

Adsorption behavior of molybdenum onto D314 ion exchange resin

The adsorption behavior of molybdenum onto D314 was studied with the static adsorption method. The adsorption process was analyzed from thermodynamic and kinetic aspects. The experimental results show that the equilibrium adsorption data conform satisfactorily to the Langmuir equation. In the adsorption process of D314 for molybdenum, the enthalpy change ΔH is positive when temperature is in the range of 298-338 K, which indicates that the adsorption is an endothermic process, and the elevated temperature benefits to the adsorption. Kinetic analysis shows that the adsorption rate is controlled by intraparticle diffusion and chemical diffusion at the same time. The adsorption mechanism of molybdenum onto D314 was discussed based on IR spectra.

The Removal of Chromium(VI) from Aqueous Solution by Amine-Functionalized Zeolite: Kinetics, Thermodynamics, and Equilibrium Study

In this study, the removal of Cr(VI) from aqueous solution by modified zeolite with 3-aminopropyltriethoxysilane was investigated. The effect of various parameters such as pH, contact time, temperature, initial concentration of Cr(VI) ion, common cations, and anions on the adsorption of Cr(VI) was studied. The modified zeolite was characterized by following instrumental analysis of XRD, SEM/EDS, BET, and FT-IR. Based on calculated thermodynamic parameters values (ΔG0 < 0, ΔH0 > 0, and ΔS0 > 0) and kinetic properties of the adsorption of Cr(VI) by modified zeolite, it was concluded that the rate-limiting step of the process is a second-order chemical reaction. The results of the adsorption isotherm study confirmed that the adsorption follows the Langmuir isotherm model. The maximum adsorption capacity was 13.5 mg/g.

Thermodynamic study of adsorption of phenolic compounds onto Amberlite XAD-4 polymeric adsorbents and its acetylized derivative MX-4

Adsorption equilibrium isotherms of phenolic compounds, phenol, p cresol, p chlorophenol and p nitrophenol, from aqueous solutions by Amberlite XAD 4 polymeric adsorbent and its acetylized derivative MX 4 within temperature range of 283 323K were obtained and fitted to the Freundlich isotherms. The capacities of equilibrium adsorption for all four phenolic compounds from their aqueous solutions increased around 20% on the acetylized resin, which may be contributed to the specific surface area and the partial polarity on the network. Estimations of the isosteric enthalpy, free energy, and entropy for the adsorption process were reported.

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p- nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.

Kinetic and Thermodynamic Studies on Raney Ni/Al2O3 Adsorption for Deep Desulfurization of Benzene Stream

How to remove trace amount of sulfur in benzene is of significance,and deep desulfurization by Ni-containing absorbents is an efficient and promising method.In this paper,The Raney Ni/Al2 O3 adsorbent was prepared and its kinetic and thermodynamic characteristics on adsorptive desulfurization of benzene were studied.The results showed that Raney Ni/Al2 O3 adsorbent exhibited good adsorption performance.The equilibrium isotherms indicated that the adsorption of thiophene over the Raney Ni/Al2 O3 adsorbent complied with the Freundlich model.The results of adsorption kinetics studies showed that the pseudo-second-order kinetics equation was more advantageous than the pseudo-first-order kinetics equation in describing the adsorption kinetics of thiophene on Raney Ni/Al2 O3.The rate constant value(kp)was positively correlated with the temperature whereas the adsorption mass transfer process was mainly determined by the intraparticle and film diffusion.The adsorption thermodynamic analysis proved that△G^0<0,△H^0>0,and△S^0>0,implying that the adsorption was a spontaneous,entropy-increasing and endothermic process.

Thermodynamic and Kinetic Studies of Effective Adsorption of 2,4,6-trichlorophenol onto Calcine Mg/Al-CO_3 Layered Double Hydroxide

Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powder X-ray diffraction（XRD） and thermo gravimetric analyzer-differential scanning calorimeters（TG-DSC）. Moreover, 2,4,6-trichlorophenol（TCP） was removed effectively（94.7% of removal percentage in 9h） under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.

Preparation of Waste Coffee-grounds Carbon and Study on Phenol Adsorption Ability

The waste coffee-grounds carbon(WCGC)was prepared with H_(3)PO_(4)treated using waste coffee-grounds as precursor.Its adsorption ability was studied using phenol as test molecule.The influence of H_(3)PO_(4)treated,calcined temperature,the initial phenol concentration,the doge of carbon and original pH values on phenol adsorption ability were investigated.Characterization of WCGC was performed by N_(2)adsorption isotherms,Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),and X-ray diffraction(XRD)techniques.First,the second order and Weber-Morris model reaction rate models were used to estimate the WCGC adsorption ability.The results show that the produced WCGC(700℃,2 h)has been graphitized and the layered structure increased BET surface to 435.98 m^(2)/g and adsorption phenol ability.The initial phenol concentration is 50 mg/L,the amount of WCGC(700℃,2 h)is 0.2 g,and the phenol adsorption rate is 97%after 270 min and no intermediate product formation.The adsorption kinetics of the selected WCGC is best fitted by the Weber-Morris model.

K^+ Adsorption Kinetics of Fluvo-Aquic and Cinnamon Soil Under Different Temperature

The K+ adsorption kinetics of fluvo-aquic soil and cinnamon soil under different temperatureswere studied. The results showed: 1) The first order equations were the most suitable forfitting the adsorption under various temperature levels with constant K+ concentration indisplacing fluid. With temperature increasing, the fitness of Elovich equation increased,while those of power equation and parabolic diffusion equation decreased; 2)the apparentadsorption rate constant ka and the product of ka multiplied by the apparent equilibriumadsorption qincreased when temperature increased, while the apparent equilibrium adsorptionqreduced; 3)temperature influenced hardly the reaction order, the order of concentrationand adsorpton site were always 1 under various temperatures, if they were taken intoaccount simultaneously, the adsorption should be a two-order reaction process; 4)theGibbs free energy change △G of potassium adsorption were negative, ranged from -4444.56to -2450.63Jmol-1,and increased with temperature increasing, while enthalpy change △H,entropy change △S, apparent adsorption activation Ea, adsorption activation energy E1and desorption activation energy E2 were temperature-independent; 5)the adsorption wasspontaneous process with heat releasing and entropy dropping, fluvo-aquic soil releasedmore heat than cinnamon soil.

Synthesis of a novel functional group-bridged magnetized bentonite adsorbent:Characterization,kinetics,isotherm,thermodynamics and regeneration

A novel magnetic adsorbent was synthesized by magnetizing bentonite by APTES-Fe_3O_4 via a functional groupbridged interaction. The characterization of APTES-Fe_3O_4/bentonite was conducted via transmission electron microscope(TEM), X-ray diffraction(XRD), Fourier transform infrared spectrophotometer(FT-IR), thermal gravimetric analysis(TGA), vibrating sample magnetometer(VSM), zeta potential analysis and Brunner–Emmet–Teller(BET). The APTES-Fe_3O_4/bentonite was assessed as adsorbents for methylene blue(MB) with a high adsorption capacity(91.83 mg·g^(-1)). Factors affecting the adsorption of MB(such as p H, equilibrium time, temperature and initial concentration) were investigated. The adsorption process completely reaches equilibrium after 120 min and the maximum sorption is achieved at p H 8.0. The adsorption trend follows the pseudosecond order kinetics model. The adsorption data gives good fits with Langmuir isotherm model. The parameter factor RLfalls between 0 and 1, indicating the adsorption of MB is favorable. The adsorption process is endothermic with positive ΔH^0 values. The positive values of ΔG^0 confirm the affinity of the adsorbent towards MB, and suggest an increased randomness at the solid–liquid interface during the adsorption process. Regeneration of the saturated adsorbent was easily carried out via gamma-irradiation.

THE ADSORPTION BEHAVIORS OF 2,6-DICHLOROPHENOL ONTO HYPERCROSSLINKED RESINS

Experimental investigations were conducted on the adsorption characteristics of 2,6-dichlorophenol by two hypercrosslinked resins ZH-01 and XAD-4. The static adsorption was studied. Within temperature range of 288K-313K, the equilibrium adsorption date was fitted to freundlich adsorption isotherm models to evaluate the model parameters. The enthalpies, free energy, entropy were indicative of an exothermic, a spontaneous and disorder decreasing process. The magnitudes for 2,6-dichlorophenol on ZH-01 showed a chemisorption＇s transitions while on XAD-4 shows a physical adsorption process. The results showed that the ZH-01 adsorbents were better than the Amberlite XAD-4 for removing the 2,6-dichlorophenol in aqueous solutions.

Adsorption of herring sperm DNA onto pine sawdust biochar:Thermodynamics and site energy distribution

Environmental deoxyribonucleic acid(eDNA),which includes antibiotic resistance genes,is ubiquitous in the environment.The interactions between eDNA and biochar,a promising material widely used in soil amendment and water treatment,greatly affect the environmental behavior of eDNA.Hitherto few experimental evidences are available yet,especially on the information of thermodynamics and energy distribution to explains the interactions between biochar and eDNA.This study investigated the adsorption of herring sperm DNA(hsDNA)on pine sawdust biochar,with a specific emphasis on the adsorption thermodynamics and site energy distribution.The adsorption of hsDNA on biochar was enhanced by an increase in the pyrolysis and adsorption temperatures.The higher surface area,strongerπ−πinteraction,and weaker electrostatic repulsion between hsDNA and biochars prepared at high pyrolysis temperatures facilitated the adsorption of hsDNA.The thermodynamics indicated that the adsorption of hsDNA on biochar was spontaneous and endothermic.Therefore,higher temperature was beneficial for the adsorption of hsDNA on biochar;this was well explained by the increase in E*and F(E*)with the adsorption temperature.These results are useful for evaluating the migration and transformation of eDNA in the presence of biochar.

Anti-adsorption mechanism of ion-adsorption type rare earth tailings

To investigate the process of RE^(3+)anti-adsorption on ion-adsorption type rare earth tailings,the thermodynamics,adsorption kinetics and infrared spectroscopy of these materials were investigated.The results indicate that the initial reaction rate of anti-adsorption of rare earth tailings is fast,but it reaches a balance in 6 min.The formula 1-2a/3-(1-a)2/3=k_2t(k represents rate constant of the reaction,a represents anti-adsorption rate of rare earth ore,t represents anti-adsorption time)of internal diffusion can be used to predict the kinetics of anti-adsorption in IATRE tailings.BecauseΔH<0,ΔG<0,ΔS>0(ΔH,ΔG,ΔS represent change of enthalpy,Gibbs free energy and entropy,respectively),the anti-adsorption of RE^(3+)on ion-adsorption type RE tailings is a spontaneous physical adsorption process.The effects of ligand exchange and strong chemical bond are not found in this process.Because the anti-adsorption process is exothermic,heating will inhibit the reaction and decrease the anti-adsorption performance.According to the infrared spectrum analysis,there are no significant changes in the mineral surface after anti-adsorption.Based on these findings,the anti-adsorption of rare earth tailings is physical adsorption.

Preparation and utilization of wheat straw anionic sorbent for the removal of nitrate from aqueous solution

In order to reduce the impact of eutrophication caused by agricultural residues （i.e., excess nitrate） in aqueous solution, economic and effective anionic sorbents are required. In this article, we prepared anionic sorbent using wheat straw. Its structural characteristics and adsorption properties for nitrate removal from aqueous solution were investigated. The results indicate that the yield of the prepared anionic sorbent, the total exchange capacity, and the maximum adsorption capacity were 350%, 2.57 mEq/g, and 2.08 mmol/g, respectively. The Freundlich isotherm mode is more suitable than the Langmuir mode and the adsorption process accords with the first order reaction kinetic rate equation. When multiple anions （SO4^2-, H2PO4^-, NO3^-, and NO2^-） were present, the isotherm mode of prepared anionic sorbent for nitrate was consistent with Freundlich mode; however, the capacity of nitrate adsorption was reduced by 50%. In alkaline solutions, about 90% of adsorbed nitrate ions could be desorbed from prepared anionic sorbent. The results of this study confirmed that the wheat straw anionic sorbent can be used as an excellent nitrate sorbent that removes nitrate from aqueous solutions.