Analysis of CH_(4) and H_(2) Adsorption on Heterogeneous Shale Surfaces Using aMolecular Dynamics Approach

Determining the adsorption of shale gas on complex surfaces remains a challenge in molecular simulation studies.Difficulties essentially stem from the need to create a realistic shale structure model in terms of mineral heterogeneityand multiplicity.Moreover,precise characterization of the competitive adsorption of hydrogen andmethane in shale generally requires the experimental determination of the related adsorptive capacity.In thisstudy,the adsorption of adsorbates,methane(CH_(4)),and hydrogen(H_(2))on heterogeneous shale surface modelsof Kaolinite,Orthoclase,Muscovite,Mica,C_(60),and Butane has been simulated in the frame of a moleculardynamic’s numerical technique.The results show that these behaviors are influenced by pressure and potentialenergy.On increasing the pressure from 500 to 2000 psi,the sorption effect for CH_(4)significantly increasesbut shows a decline at a certain stage(if compared to H_(2)).The research findings also indicate that raw shalehas a higher capacity to adsorb CH_(4)compared to hydrogen.However,in shale,this difference is negligible.

An analytical transient coal permeability model:Sorption non-equilibrium index-based swelling switch

Long-term permeability experiments have indicated that sorption-induced swelling can switch from internal to bulk depending on the evolutive sorption status.However,this sorption swelling switch mechanism has not been considered in current analytical permeability models.This study introduces a normalized sorption non-equilibrium index(SNEI)to characterize the sorption status,quantify the dynamical variations of matrix swelling accumulation and internal swelling partition,and formulate the sorption swelling switch model.The incorporation of this index into the extended total effective stress concept leads to an analytical transient coal permeability model.Model results show that the sorption swelling switch itself results in the permeability switch under stress-constrained conditions,while the confined bulk swelling suppresses the permeability recovery to the continuous reduction under displacement-constrained conditions.Model verifications show that current experimental observations correspond to the early stages of the transient process,and they could be extended to the whole process with these models.This study demonstrates the importance of the sorption swelling switch in determining permeability evolution using simple boundary conditions.It provides new insights into experimentally revealing the sorption swelling switch in the future,and underscores the requirement of a rigorous model for complex coupled processes in large-scale coal seams.

The Al_(2)O_(3)and Mn/Al_(2)O_(3)sorbents highly utilized in destructive sorption of NF_(3)

NF_(3)is commonly used as an etching and cleaning gas in semiconductor industry,however it is a strongly greenhouse gas.Therefore,the destruction of disposal NF_(3)is an urgent task to migrate the greenhouse effect.Among the technologies for NF_(3)abatement,the destructive sorption of NF_(3)over metal oxides sorbents is an effective way.Thus,the search for a highly reactive and utilized sorbent for NF_(3)destruction is in great demand.In this work,AlOOH supported on carbon-sphere(AlOOH/CS)as precursors were synthesized hydrothermally and heat-treated to prepare the Al_(2)O_(3)sorbents.The influence of AlOOH/CS hydrothermal temperatures on the reactivity of derived Al_(2)O_(3)sorbents for NF_(3)destruction was investigated,and it is shown that the Al2O3 from AlOOH/CS hydro-thermalized at 120℃is superior to others.Subsequently,the optimized Al_(2)O_(3)was covered by Mn(OH)x to prepare Mn/Al_(2)O_(3)sorbents via changing hydrothermal temperatures and Mn loadings.The results show that the Mn/Al_(2)O_(3)sorbents are more utilized than bare Al_(2)O_(3)in NF_(3)destructive sorption due to the promotional effect of Mn_(2)O_(3)as surface layer on the fluorination of Al_(2)O_(3)as substrate,especially the optimal 5%Mn/Al2O3(160℃)exhibits a utilization percentage as high as 90.4%,and remarkably exceeds all the sorbents reported so far.These findings are beneficial to develop more efficient sorbents for the destruction of NF_(3).

SYNTHESIS，REGENERATION AND APPLICATIONOF SORPTION RESINS

By means of the synthetic approach of non－polar or weak polar oil－sorbed polymers，the gel sorption resin（GSR） and the multiporous sorption resin（MSR） were prepared．The structure of the resins，sorption power，sorption speed，desorption，and sorption of organic compounds from sewage，exhaust gas and soil were discussed．Moreover，the resins were used to decrease LOD and BOD5 values of water waste from sewage factory．Theyare a klndof potential materials for environmental control．

Enhanced and irreversible sorption of pesticide pyrimethanil by soil amended with biochars

Biochar derived from partial combustion of vegetation is ubiquitous and potentially effective in sequestration of environmental contaminants. Biochars were prepared by burning of red gum （Eucalyptus spp.） woodchips at 450 and 850℃ （labeled as BC450 and BC850）. These two biochars were found to possess markedly different properties in terms of surface area and porosity. Short-term equilibration tests （24 hr） were conducted to assess the sorption-desorption behavior of pyrimethanil in the soil amended with various amounts of biochar of each type, with a special focus on the desorption behavior of the sorbed pesticide through four times successive desorption by dilution. Sorption coefficient and isotherm nonlinearity of the amended soils progressively increased with the content of biochar in the soil. Biochar BC850 with higher surface area and microporosity showed a stronger effect on the reversibility of sorption pesticide. The soils amended with 5% BC450 and 1% BC850 had nearly the same sorption capacity for pyrimethanil; however, their desorption processes were very different with 13.65% and 1.49% of the sorbed pesticide being released, respectively. This study suggested that biochar in soil could be an important factor for immobilization of a pesticide and thus affecting its environment fate in soil.

Impacts of soil organic matter, pH and exogenous copper on sorption behavior of norfloxacin in three soils

Norfloxacin sorption and the factors （soil organic matter （SOM）, pH, and exogenous copper （Cu） influencing the sorption were investigated in a black soil （soil B）, a fluvo-aquic soil （soil F）, and a red soil （soil R）. With increasing norfloxacin concentrations, sorption amount of norfloxacin increased in both the bulk soils and their SOM-removed soils, but the sorption capacity of SOM-removed soils was higher than that of their corresponding bulk soils, indicating that the process of norfloxacin sorption in soil was influenced by the soil properties including SOM. The sorption data in all bulk soils and SOM-removed soils were fitted to Freundlich and Langmuir models. The correlation coefficients suggested that the experimental data fitted better to Freundlich equation than to Langmuir equation. Furthermore, the data from soil F and SOM-removed F could not be described by Langmuir equation. The norfloxacin sorption amount decreased in soil B and soil F, whereas it increased in soil R as solution pH increased. The maximum KD and Koc were achieved in soil R when the equilibrium solution pH was 6. The norfloxacin sorption was also influenced by the exogenous Cu^2＋, which depended on the soil types and Cu^2＋ concentrations. With increasing Cu^2＋ concentrations in solution, generally, sorption amount, KD and Koc for norfloxacin in soils increased and were up to a peak at 100 mg/L Cu^2＋, and then the sorption amount decreased regardless of norfloxacin levels.

Effect of temperature on the sorption and desorption of perfluorooctane sulfonate on humic acid

Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be –7.11 to –5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/（mol·K）, indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.

Effects of temperature and surfactants on naphthalene and phenanthrene sorption by soil

Adsorption experiments were carried out to investigate the sorption behaviors of naphthalene and phenanthrene in six different soils and to determine the effects of temperature, linear alkylbenzene sulfonate （LAS） and cetylrimethyl ammonium bromide （CTAB） on sorption. The results show that for a given sorbent phenanthrene exhibited greater nonlinear and stronger sorption than naphthalene. There was a strong negative correlation for the Koc values with organic carbon content （foc）. The increase of temperature was not favorable to sorption. Sorption decreased along with the increasing aqueous LAS concentration from 0 to 1000 mg/L. At low CTAB concentration （〈 100 mg/L）, the adsorption increased as CTAB hemimicelles formed on the soil surface. At high concentration, CTAB decreased the adsorption by occupying active hydrophobic adsorption sites and solubilization of naphthalene and phenanthrene.

Sorption of dissolved organic matter and its effects on the atrazine sorption on soils

The dissolved organic matter(DOM), water soluble organic matter derived from sewage sludge was separated into hydrophobic fraction(Ho) and hydrophilic fraction(Hi). The sorption of DOM and its fractions on soils and the effects of DOM sorption on a nonionic pesticide(atrazine(2-chloro-4-ethylamino-6-isopropylamino-1,3,5-trazine)) distribution between soil and water were investigated using a batch equilibrium technique. The total DOM sorption on soils described by the Langmuir equation reached saturation as the DOM concentration increased. The sorption of Ho fit the Freundlich model. In contrast, a negative retention evidently occurred as adding Hi at higher level in tested soils. The sorption of Ho dominated the total DOM sorption and the release of soil organic matter(SOM). Effects of DOM on the atrazine sorption by soils were DOM-concentration dependent and dominated by the interaction of atrazine, DOM, and soil solids. Generally, the presence of DOM with lower concentration promoted atrazine sorption on soils, namely the apparent partitioning constant(K*_d) for atrazine sorption in the presence of DOM was larger than the distribution constant(K_d) without DOM; whereas the presence of DOM with higher concentration inhibited atrazine sorption(i.e., K*_d<K_d). The overall effects of DOM on atrazine sorption in soils might be related to the DOM sorption and the release of soil intrinsic organic matter into aqueous solution. The sorption of Ho on soils promoted the atrazine sorption on soil, while the release of SOM by Hi and the competitive sorption between Hi and atrazine on soil surface led to a decrease of atrazine sorption. Information provided in this work may contribute to a better understanding of the DOM sorption and its impacts on the contaminant soil-water distribution.

Adsorption of Er(Ⅲ ) and Its Mechanism on Diglycolamidic Acid Resin

The adsorption behavior and mechanism of a novel chelate resin, diglycolamidic acid resin (DAAR) for Er(Ⅲ) were investigated. The optima adsorption condition of DAAR for Er(Ⅲ) is pH 6.20 in HAc NaAc medium. The statically saturated adsorption capacity is 189 mg·g -1 resin at 298 K. The Er (Ⅲ) adsorbed on DAAR can be eluted reaching 100% by 2 mol·L -1 HCl used as eluant. The resin can be regenerated and reused without apparent decreasing of adsorption capacity. The apparent adsorption rate constant is k 298 =1.94×10 -5 s -1 . The apparent activation energy is 24.7 kJ·mol -1 . The adsorption behavior of DAAR for Er(Ⅲ) obeys the Freundlich isotherm. The thermodynamic adsorption parameters, enthalpy change Δ H of DAAR for Er(Ⅲ) is 24.1 kJ·mol -1 . The molar coordination ratio of the functional group of DAAR to Er (Ⅲ) is 3∶1. The adsorption mechanism of DAAR for Er (Ⅲ) was examined by using chemical method and IR spectrometry. The coordination compound is formed between oxygen atoms in the functional group of DAAR and Er(Ⅲ).

A Combination of N2 and CO2 Adsorption to Characterize Nanopore Structure of Organic-Rich Lower Silurian Shale in the Upper Yangtze Platform, South China： Implications for Shale Gas Sorption Capacity

The pores in shales are mainly of nanometer-scale, and their pore size distribution is very important for the preservation and exploitation of shale gas. This study focused on the organic-rich Lower Silurian black shale from four wells in the Upper Yangtze Platform, and their TOC, mineralogical composition and pore characterization were investigated. Low pressure N2 and CO2 adsorption were conducted at 77.35 K and 273.15 K, respectively, and the pore structures were characterized by modified Brunauer-Emmett-Teller （BET）, Dubinin-Radushkevich （DR）, t-plot, Barrett- Joyner-Halenda （BJH） and density functional theory （DFT） methods and then the relationship between pore structure and shale gas sorption capacity was discussed. The results indicate that （1） The Lower Silurian shale has high TOC content of 0.92%~96%, high quartz content of 30.6%-69.5%, and high clays content of 24.1%-51.2%. The total specific surface area varies from 7.56 m^2/g to 25.86 m^2/g. Both the total specific surface area and quartz content are positively associated with the TOC content. （2） Shale samples with higher TOC content have more micropores, which results in more complex nanopore structure. Micropore volumes/surface areas and non-micropore surface areas all increase with the increasing TOC content. （3） A combination of N2 and CO2 adsorption provides the most suitable detection range （~0.3-60 nm） and has high reliability and accuracy for nanopore structure characterization. （4） The TOC content is the key factor to control the gas sorption capacity of the Lower Silurian shale in the Upper Yangtze Platform.

Sorption of Heavy Metal and Organic Pollutants on Modified Soils

Sorption characteristics of both an organic pollutant (phenol) and a heavy metal (cadmium ion) on the clay layer of a Lou soil (Eum-orthic Anthrosol in Chinese Soil Taxonomy) along with the sorption mechanism were investigated using three soil treatments: modification with a cationic surfactant cetyltrimethylammonium bromide added at an amount equivalent to 50% and 100% of the soil CEC (50%CB and 100%CB), modification with an amphoteric surface-modifying agent dodecyldimethylbetaine (commercially known as BS-12) added at an amount equivalent to 50% and 100% of the soil CEC (50% BS and 100%BS), and an unmodified control (CK). Results showed that the BS soil treatments increased sorption of both the heavy metal Cd2+ and the organic pollutant phenol. The equilibrium sorption amount of Cd2+ decreased in the order: 50%BS > 100%BS > CK > 50%CB > 100%CB, with the BS soil treatments being about 1.3 to 1.8 times higher and the CB soil treatments about 23% to 41% lower than CK. Both the single-site and two-site Langmuir models could be applied to describe the sorption of Cd2+ in each soil treatment. The equilibrium sorption amount of phenol on the soil samples decreased in the order: 100%CB > 50%CB > 100%BS > 50%BS > CK, with the CB soil treatments being 41.0 to 79.6 times higher and the BS soil treatments 4.0 to 8.3 times higher than CK. The Freundlich equation could also be used to describe the sorption characteristics of phenol. In the BS soil treatments, both an organophobic long carbon chain and hydrophilic charged groups resulted in a relatively strong sorption ability for both heavy metals and organic pollutants. In addition, the sorption ratio K, the ratio of phenol sorption amount of the modified soil to that of CK, increased initially and decreased later with the amount of phenol added, and the critical sorption ratio KC, the peak value of the sorption ratio curve plotted against the added phenol concentration, was a good index for evaluating the sorption ability of phenol in the soil.

Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis Dehn. bark

Powdered activated carbon (PAC) prepared from Eucalyptus camaldulensis Dehn. bark was tested for its adsorption capacity for Cu(Ⅱ) and Pb(Ⅱ). The experiment was conducted to investigate the effects of pH, contact time, initial metal concentration, and temperature. The best adsorption of both Cu(Ⅱ) and Pb(Ⅱ) occurred at pH 5, where the adsorption reached equilibrium within 45 min for the whole range of initial heavy metal concentrations (0.1-10 mmol/L). The adsorption kinetics was found to follow the pseudo-...

Effects of Mo on the Microstructure and Hydrogen Sorption Properties of Ti-Mo Getters

The effects of Mo on the microstructure evolution, porosity and hydrogen sorption properties of Ti-Mo getters are investigated in this work. The results show that the addition of Mo prolongs the densification process of Ti-Mo getters and results in a significant amount of sintered pores. With the Mo content increasing, the porosity of getters firstly increases reaching the maximum value as it attains about 7.5wt.%, and then drops. At the room temperature, the hydrogen sorption property of getters increases progressively with the Mo content increasing, but the tendency is not very clear before its content lies below 2.5wt.%. When the Mo content achieves about 7.5wt.%, the hydrogen sorption property proves to be the best. The discussion is made about the above mentioned phenomena inclusive of hydrogen sorption properties of getters under different activation conditions （from 500-750℃）.

Sorption of Triton X-100 on soil organic matter fractions:Kinetics and isotherms

Kinetics and isotherms of Triton X-100 sorption on soil,base-extracted soil（BE）,humic acid（HA） and humin（HM） were investigated respectively to get better understanding on characteristics of the surfactant sorption onto different soil organic matters（SOMs）.It was demonstrated that the kinetics results could be satisfactorily described by the pseudo-second order model.The half of the time to reach equilibrium（t1/2） for different sorbents followed the sequence of soil 〉 HA 〉 BE 〉 HM.Furthermore,the calculated equilibrium sorption capacity（Ceq） was found in the sequence of HA 〉 BE 〉 HM 〉 soil,which agreed well with the experimental results.The isotherms of Triton X-100 sorption on soil and HA could be well described by the S-type isotherm,but BE and HM by the L-type.The isotherms of all the four sorbents were found reasonably fitted to the Langmuir equation.The Kd value,defined as the ratio of Triton X-100 in sorbent and in the equilibrium solution for given concentrations,generally followed the order of HM 〉 HA 〉 soil 〉 BE.Separated HM and HA showed high affnity for Triton X-100,but the HA and HM in soil and BE were tightly bounded by the minerals.Thus,the HA on the soil surface might dominate the sorption,whereas the bounded HM would play a key role upon the surfactants being penetrated inside the soil.

Effects of dissolved organic matter from sewage sludge on sorption of tetrabromobisphenol A by soils

Sorption of tetrabromobisphenol A (TBBPA) by soil influences its fate and transport in the environment. The presence of dissolved organic matter (DOM) may complicate the sorption process in soil. The effects of DOM from sewage sludge on TBBPA sorption by three soils were investigated using batch equilibration experiments in the study. DOM was observed to be sorbed on the soils and the isotherms could be fitted by the Langmuir model. The effects of DOM on TBBPA sorption were dependent on the characteristics ...

Effect of pH on sorption for RE(III) and sorption behaviors of Sm(III) by D152 resin

The pH dependent sorption of rare earth ions （La（Ⅲ）, Ce（Ⅲ）, Pr（Ⅲ）, Nd（Ⅲ）, Y（Ⅲ）, Sm（Ⅲ）, Eu（Ⅲ）, Gd（Ⅲ）, Tb（Ⅲ）, Dy（Ⅲ）, Ho（Ⅲ）, Er（Ⅲ）, Lu（Ⅲ）, and Yb（Ⅲ）） from HAC-NaAC buffer solution at 298 K by D152 resin containing -COOH function groups were presented. The sorption behaviors of D152 resin for Sm（Ⅲ） were discussed as an example. The effects of operational conditions such as pH, temperature, and contact time were studied. The statically saturated sorption capacity was 510 mg/g resin at pH 6.70 in HAc-NaAc medium at 298 K. The sorption behaviors obeyed the Freundlich isotherm. The capacity value for column study was obtained by graphical integration as 495 mg/g resin. Thomas model was applied to experimental data to predict the breakthrough curve and to determine the characteristic parameters of the column useful for process design.

Kinetics study of aqueous sorption of phenanthrene to humic acids and sediments

The sorption behavior was determined for a model polycyclic aromatic hydrocarbon(PAH), i.e., phenanthrene(PHN), from water to three humic acids(HAs) and three sediments in different reacting time. The chemical compositions of HA samples were measured using cross polarization magic angle spinning carbon 13(CPMAS 13 C NMR along with elemental analysis. The dissolved humic substances dissociating from solid HAs and sediments were characterized by 1 H NMR. The experiments indicated that the sorption modes and mechanisms of natural sorbents for PHN varied significantly between short(<7 d) and long contact time and the reaction time should be taken into consideration in studying the overall sorption process. The sorption capacity( K ′ f) and exponent( n ) might be relative to the properties of dissolved humic materials in initial stage but the solid aromatic organic matter after long time reaction. According to the experiments performed in this investigation and the previous researches, a conceptive sorption model was established.

Numerical modeling of radionuclide migration in porous media with nonequilibrium sorption

When radionuclides migrate in porous media with water serving as carrier, the mechanism of sorption and desorption is not negligible. nonequilibrium conditions exist in sorption and desorption. In this paper,a numerical model of radionuclide migration with nonequilibrium sorption was developed.The algorithm of numerical descretizing and direct substituting was adopted in coupling of the convective-dispersive equation and the nonequilibrium sorption isotherm in this model ,and this makes it easier to solve the model numerically.A quantitative analysis is made for the first time that the influence of nonequilibrium sorption, represented by the rate coefficient which shows how quickly the nonequilibrium condition in sorption and desorption reaches equilibrium on the migration of radionuclide,and results show that it affects the migration perceptibly. Finally the model was verified by using the observed data of radionuclide migration test conducted in the field, and which clarified its availability.

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene （m-DNB） and nitrobenzene to original bentonite in aqueous solution containing different electrolytes （i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide （TMAB）） was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl 〉 NH4Cl 〉〉 TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out effect is insufficient to account for the sorption enhancement by original bentonite with increasing KCI or NH4Cl concentration. X-ray diffraction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K^＋ or NH4^＋ into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K^＋ at high solute-loadings （〉 20（0-400 mg/kg）. The sorption of m-DNB to initially modified TMA^＋-bentonite and K^＋-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA^＋ and K^＋.