Molecular mechanism of adsorption/desorption hysteresis:dynamics of shale gas in nanopores

Understanding the adsorption and desorption behavior of methane has received considerable attention since it is one of the crucial aspects of the exploitation of shale gas.Unexpectedly,obvious hysteresis is observed from the ideally reversible physical sorption of methane in some experiments.However,the underlying mechanism still remains an open problem.In this study,Monte Carlo(MC) and molecular dynamics(MD) simulations are carried out to explore the molecular mechanisms of adsorption/desorption hysteresis.First,a detailed analysis about the capillary condensation of methane in micropores is presented.The influence of pore width,surface strength,and temperature on the hysteresis loop is further investigated.It is found that a disappearance of hysteresis occurs above a temperature threshold.Combined with the phase diagram of methane,we explicitly point out that capillary condensation is inapplicable for the hysteresis of shale gas under normal temperature conditions.Second,a new mechanism,variation of pore throat size,is proposed and studied.For methane to pass through the throat,a certain energy is required due to the repulsive interaction.The required energy increases with shrinkage of the throat,such that the originally adsorbed methane cannot escape through the narrowed throat.These trapped methane molecules account for the hysteresis.Furthermore,the hysteresis loop is found to increase with the increasing pressure and decreasing temperature.We suggest that the variation of pore throat size can explain the adsorption/desorption hysteresis of shale gas.Our conclusions and findings are of great significance for guiding the efficient exploitation of shale gas.

Study on the Effects of Polyacrylamide on Phosphorus Adsorption and Desorption Characteristics of Soil Aggregates

[Objective]The research aimed to provide scientific reference for reasonable utilization of polyacrylamide(PAM).[Method]After PAM treatment,the soil aggregates were classified through dry sieve analysis and the adsorption capacity and desorption capacity of all soil aggregates to phosphorus at different phosphorus concentrations were analyzed.[Result] The phosphorus adsorption and desorption of soil sample treated by PAM declined. The amount of phosphorus adsorption increased with the increase of phosphorus concentration and this increase was fast in low phosphorus concentration area but slow in high phosphorus concentration area.At different phosphorus concentrations,adsorption showed a へ shape changing trend.The phosphorus adsorption was related to phosphorus concentration and the 2-3 mm aggregate had the highest desorption rate while 0.1-0.25 mm aggregate and 0.45-1 mm aggregate had lowest desorption rate.[Conclusion]The PAM treatment generated significant influence on phosphorus adsorption and analytic features of aggregate in all size fractions.

Adsorption and Desorption Characteristics of Cadmium and Lead in Typical Paddy Soils of Jiangxi Province and Its Environmental Risk Assessment

[Objective] This study aimed to investigate the adsorption and desorption characteristics of cadmium and lead in typical paddy soils of Jiangxi Province. [Method] Gleyed paddy soil and waterloggogenic paddy soil were collected from Jiangxi Province and used as experimental materials to investigate single and com- petitive adsorption and desorption behaviors of cadmium and lead by batch equilib- rium method. The environmental risk of the presence of cadmium and lead in paddy soils was assessed using distribution coefficients. [Result] Under equal ratio condi- tions, the adsorption capacity of lead by two types of paddy soils was higher than that of cadmium, and the adsorption rate in waterloggogenic paddy soil was higher than that in gleyed paddy soil. The desorption capacity of cadmium by two types of paddy soils was higher than that of lead, and the desorption rate in gleyed paddy soil was higher than that in waterloggogenic paddy soil. Under competitive condi- tions, the adsorption capacity of cadmium and lead by paddy soils was significantly reduced compared with single ion system, while the desorption rate was remarkably improved. The potential environmental risk of cadmium contamination was greater than that of lead in paddy soils. Moreover, environmental risks of cadmium and lead were reduced with the increase of pH, which increased significantly under the coex- istence state. [Conclusion] In the coexistence of cadmium and lead, cadmium con- tamination should be controlled and avoided compared with lead contamination in paddy soils.

Adsorption and Desorption of Natural Zeolite on NH_4^+

The adsorption and desorption kinetic of natural zeolite on NH4＋ was stud-ied by lab analysis. The results showed that the adsorption and desorption kinetic of natural zeolite on NH4＋ coincided with the first-order kinetics, modified Freundlich equation, parabolic diffusion model, and heterogeneous diffusion model. The desorp-tion of the adsorbed NH4＋ was far rapider than the adsorption, which can be fin-ished within 60 min.

Adsorption/desorption behavior between a novel amphoteric granular lignin adsorbent and reactive red K-3B in aqueous solutions

A novel amphoteric granular lignin adsorbent(AGLA) was prepared using magnesium lignosulfonate as a raw material which was provided by a straw sulfite pulp mill in Guangdong Province, China. A reactive dye(red K-3B) was used as an adsorbate to investigate the adsorption behavior by static and mobile ways. The removal of reactive red K-3B was found to be initially pH and concentration dependent. Moreover, an increase of solution temperature ranging from 5℃ to 60℃ helped to enhance the rate of intraparticle diffusion of adsorbate and changes in the size of the pores of the adsorbent and thus to reduce the adsorption time. The total breakthrough adsorption capacity was 531 mg/g, and the saturated adsorption capacity was 560 mg/g, which prevailed over the activated carbons evidently. The reactive red K-3B adsorbed on AGLA could be recovered with a mixture of alcohol, NaCl and HCl aqueous solutions. The recovery percentage could reach 92.4%.

Effect of dissolved organic matter on adsorption and desorption of mercury by soils

Effects of dissolved organic matter (DOM) on adsorption and desorption of Hg were investigated in two kinds of soils, Xanthi-Udic Ferralosols (XUF) and Typic Purpli-Udic Cambosols (TPUC). The DOM was obtained from humus soil (DOMH), rice straw (DOMR), and pig manure (DOMP). The presence of DOM obviously reduced Hg maximum adsorption capacity with up to 40% decreases over the control, being an order of DOMH (250.00 mg/kg)< DOMR (303.03 mg/kg) < DOMP (322.58 mg/kg) < CK (control 416.67 mg/kg) for the...

Adsorption and desorption of Cu(Ⅱ) and Pb(Ⅱ) in paddy soils cultivated for various years in the subtropical China

The adsorption and desorption of Cu（Ⅱ） and Pb（Ⅱ） on upland red soil,and paddy soils which were originated from the upland soil and cultivated for 8,15,35 and 85 years,were investigated using the batch method.The study showed that the organic matter content and cation exchange capacity （CEC） of the soils are important factors controlling the adsorption and desorption of Cu（Ⅱ） and Pb（Ⅱ）.The 15-Year paddy soil had the highest adsorption capacity for Pb（Ⅱ）,followed by the 35-Year paddy soil.Both the 35-Year paddy soil and 15-Year paddy soil adsorbed more Cu（Ⅱ） than the upland soil and other paddy soils.The 15-Year paddy soils exhibited the highest desorption percentage for both Cu（Ⅱ） and Pb（Ⅱ）.These results are consistent with the trend for the CEC of the soils tested.The high soil CEC contributes not only to the adsorption of Cu（Ⅱ） and Pb（Ⅱ） but also to the electrostatic adsorption of the two heavy metals by the soils.Lower desorption percentages for Cu（Ⅱ） （36.7% to 42.2%） and Pb（Ⅱ） （50.4% to 57.9%） were observed for the 85-Year paddy soil.The highest content of organic matter in the soil was responsible for the low desorption percentages for the two metals because the formation of the complexes between the organic matter and the metals could increase the stability of the heavy metals in the soils.

Adsorption-desorption behavior of acetochlor to soils in the presence of some environmental substances

The behavior of herbicide acetochlor adsorption desorption to soil in the presence of humic acid (HA), anionic surfactant sodium dodecylbenzene sulfonate (SDBS), cationic surfactant hexadecyltrimethyl ammonium bromide (HDAB) and NH 4NO 3 as a chemical fertilizer was studied. Observed acetochlor adsorption isotherm were well described using Freundlich isotherm equation, from which the desorption isotherm equation has been deduced. The deduced equation can more directly describe acetochlor desorption process. The results showed that the enhance of acetochlor adsorption capacity by solid HA was greater than by soluble HA. The presence of NH 4NO 3 can slightly enhance acetochlor adsorption to soil by comparison with that measured in NH 4NO 3 free solution. In soil water system, surfactant acetochlor interaction is very complex, and the surfactant adsorptions as well as acetochlor adsorption need to be considered. When acetochlor soil suspensions contained lower concentration SDBS or HDAB (40 mg/L), K f for acetochlor adsorption was decreased in comparison to that measured in SDBS or HDAB free solution. When acetochlor soil suspensions contained higher concentration SDBS or HDAB (corresponding 1400 mg/L or 200 mg/L), K f for acetochlor adsorption was increased in comparison to that measured in SDBS or HDAB free solution.

Coalbed methane adsorption and desorption characteristics related to coal particle size

Effects of particle size on CH4 and CO2adsorption and desorption characteristics of coals are investigated at 308 K and pressures up to 5.0 MPa.The gas adsorption and desorption isotherms of coals with particle sizes ranging from 250 μm to 840 μm are measured via the volumetric method,and the Langmuir model is used to analyse the experimental results.Coal particle size is found to have an obvious effect on the coal pore structure.With the decrease of coal particle size in the process of grinding,the pore accessibility of the coal,including the specific surface area and pore volume,increases.Hence,coal with smaller particle size has higher specific surface area and higher pore volume.The ability of adsorption was highly related to the pore structure of coal,and coal particle size has a significant influence on coal adsorption/desorption characteristics,including adsorption capacity and desorption hysteresis for CH4 and CO2,i.e.,coal with a smaller particle size achieves higher adsorption capacity,while the sample with a larger particle size has lower adsorption capacity.Further,coal with larger particle size is also found to have relatively large desorption hysteresis.In addition,dynamic adsorption performances of the samples are carried out at 298 K and at pressures of 0.1 MPa and 0.5 MPa,respectively,and the results indicate that with the increase of particle size,the difference between CO2 and CH4adsorption capacities of the samples decreases.

Adsorption/desorption of toluene on a hypercrosslinked polymeric resin in a highly humid gas stream

In many sources of volatile organic compounds (VOCs), large amounts of water vapor come from the air and the reactors. The relative humidity (RH) of exhaust gas is normally >60% and is supersaturated. Maintaining the property of adsorbent on VOCs in a highly humid gas stream is a serious industrial problem. In this study, the adsorption/desorption behavior of toluene in a micro-mesoporous polymeric resin was investigated in a highly humid environment to explore the influence of abound water vapor on resin adsorption and regeneration. This resin could selectively adsorb toluene at an RH of 80%, and its adsorption property was unaffected by the presence of water vapor. In the case of humidity saturation, the resin displayed a high adsorption capacity at a moisture content of <30%. Therefore, the polymer resin is an excellent water-resistant adsorbent of VOCs. In the regenerative experiment, the resin maintained its original adsorption capability after four adsorption/ desorption cycles of toluene purging with nitrogen gas at 120℃. The resin exhibited excellent regeneration performance at high humidity.

Adsorption and desorption behaviors of ssDNA molecules on mica surface by surface forces apparatus

An approach for studying the adsorption and desorption behaviors of single-stranded DNA（ ssDNA） molecules on the mica surface by the surface forces apparatus（ SFA） is reported,which can be used to characterize the precise thickness,configuration and mechanical properties of ssDNA layers on the mica surface at a certain buffer solution. The formation of ss DNA layers is first studied by tuning the ssDNA concentrations, and the experimental results indicate that the ss DNA concentration of 100 ng / μL is ideal for forming a ssDNA monolayer structure on the mica surface, and the hardwall value measured to be 1.04 nm under this circumstance is regarded as the thickness of the ssDNA monolayer confined on mica. The desorption behavior of ssDNA molecules from the mica surface is further studied by observing and comparing different shapes of the force-distance curves under certain conditions. It is found that the desorption of ss DNA molecules from the mica surface occurs as the monovalent salts are added into the gap buffer. It is inferred that the competition effect between monovalent and divalent salts can induce the release of ssDNA from substrate.The results also reveal that 10 mmol / L monovalent salts（ Na~＋）is sufficient for the desorption of ssDNA from mica. This work provides an applicable method to study the binding mechanism of ss DNA molecules on inorganic substrates.

Oxygen adsorption/desorption behavior of YBaCo4O7+δ and its application to oxygen removal from nitrogen

A new medium-temperature (200-400 °C) adsorbent material for oxygen removal and air separation, YBaCo4O7+δ, was prepared by the solid-state reaction method. This new adsorbent could adsorb a large quantity of oxygen in the temperature range of 200-370 °C. Adsorbed oxygen could be released by raising temperature over 400 °C or by switching the atmosphere from oxygen to nitrogen. This oxygen adsorption and desorption process had good reproducibility. Taking advantage of this unique oxygen intake/release behavior, a nitrogen purification process was investigated. The results showed that YBaCo4O7+δ material was a promising candidate for the oxygen sorption process and could be used to produce high-purity nitrogen or to remove trace oxygen from other gases.

Adsorption onto Activated Carbon Fiber Cloth and Electrothermal Desorption of Volatile Organic Compound(VOCs):A Specific Review

A general research program, focusing on activated carbon fiber cloths （ACFC） and felt for environmental protection was performed. The objectives were multiple： （i） a better understanding of the adsorption mecha- nisms of these kinds of materials; （ii） the specification and optimization of new processes using these adsorbents; （iii） the modeling of the adsorption of organic pollutants using both the usual and original approaches; （iv） applications of ACFC in industrial processes. The general question was： how can activated carbon fiber cloths and felts be used in air treatment processes for the protection of environment. In order to provide an answer, different approaches were adopted. The materials （ACFC） were characterized in terms of macro structure and internal porosity. Specific studies were performed to get the air flow pattern through the fabrics. Head loss data were generated and modeled as a fi.mction of air velocity. The performances of ACF to remove volatile organic compounds （VOCs） were approached with the adsorption isotherms and breakthrough curves in various operating conditions. Regenera- tion by Joule effect shows a homogenous heating of adsorber modules with rolled or pleated layers. Examples of industrial developments were presented showing an interesting technology for the removal of VOCs, such as dichloromethane, benzene, isopropyl alcohol and toluene, alone or in a complex mixture.

Influences of Charcoal Amendment on Adsorption-Desorption of Isoproturon in Soils

In order to prevent pesticide leaching from soil, the effects of charcoal amendment on adsorption-desorption of isoproturon in soils were studied and the mechanisms in reducing the loss of isoproturon from soils were suggested. Adsorption-desorption of isoproturon in five different particle sizes of charcoals and three different soils were studied using batch equilibration technique. The results showed that the experimental data were well fitted by the Freundlich empirical equation. Charcoal had a great adsorption capacity for isoproturon, and the smaller the particle size of charcoal, the more the adsorption of isoproturon. The amendment with charcoal could greatly improve the adsorption of isoproturon in soils. The adsorption of isoproturon in soils increased with the rate of charcoal amended （r= 0.9568＊＊, P 〈 0.01）. Desorption of isoproturon from charcoals and soils showed significant hystersis which was shown by the higher adsorption slope （1/nsds） compared to the desorption slope （1/ndes. The hysteresis effects of charcoal on desorption of isoproturon were closely correlated with the content of charcoal in the soils, and the hysteresis index （H） increased with the rate of charcoal amended. Observation of environmental scanning electron microscopy （ESEM） exhibitted the fine pore structure and special surface characteristics of the tested charcoal. Analysis of Fourier transform infrared spectra （FTIR） of isoproturon adsorbed on charcoal suggested probable bonding interactions between isoproturon and charcoal. This research suggests that charcoal amendment may be an effective management practice for controlling pesticide desorption and leaching in soils.

Adsorption and Desorption Behavior of Tannic Acid in Aqueous Solution on Polyaniline Adsorbent

Tannic acid is generally considered as one of polyphenolic pollutants, which may cause severe threats to the environment. In this study, polyaniline adsorbent was synthesized by chemical oxidation to remove tannic acid in aqueous solutions. The adsorption amount of tannic acid varied greatly with pH of solution and strong adsorption was at pH 5.8-6.7. Coexisting cations, such as Na＋, K＋, and Ca2＋, can enhance the adsorption of tannic acid on poly- aniline, which may be contributed to the electrostatic interaction between tannic acid and polyaniline. The adsorp- tion process could be well described by Langmuir model and the maximum adsorption capacity was 117.65 rag.g〈 at 35℃and pH 6.0. The thermodynamic parameters calculated from the adsorption isotherms indicate that the ad- sorption of tannic acid is spontaneous and endothermic process. The polyaniline saturated with tannic acid can be desorbed in alkaline solution and regenerated adsorbent can be used repeatedly with high adsorption capacity, which implies that polyaniline adsorbents have a great potential in water purification for the removal of tannic acid.

Removal of Toluene by Adsorption/Desorption Using Ultra-stable Y Zeolite

The adsorption performance of toluene on ultra-stable Y zeolite (USY) was studied via dynamic adsorption. The eff ects of bed temperature, initial concentration, and feed fl ow rate on adsorption were investigated. The Yoon-Nelson model was used to fi t the toluene breakthrough curves. The length of mass transfer zone was calculated based on breakthrough curves. The Langmuir-Freundlich model fi t the adsorption isotherms of toluene on USY, which indicated that the surface of USY was heterogeneous. The adsorption isosteric heat calculated from adsorption isotherms ranged from 54.3 to 69.8 kJ/mol, indicating physical adsorption. The combined technique of temperature swing adsorption with vacuum swing adsorption (TVSA) exhibited excellent desorption performance, which was attributed to the low desorption activation energy. Under optimized TVSA conditions, the desorption rate of toluene reached 90.6% within 10 min. The long-term cyclic utilization results indicated that the adsorption capacity of USY was stable.

Mechanism model for shale gas transport considering diffusion, adsorption/desorption and Darcy flow

To improve the understanding of the transport mechanism in shale gas reservoirs and build a theoretical basic for further researches on productivity evaluation and efficient exploitation, various gas transport mechanisms within a shale gas reservoir exploited by a horizontal well were thoroughly investigated, which took diffusion, adsorption/desorption and Darcy flow into account. The characteristics of diffusion in nano-scale pores in matrix and desorption on the matrix surface were both considered in the improved differential equations for seepage flow. By integrating the Langmuir isotherm desorption items into the new total dimensionless compression coefficient in matrix, the transport function and seepage flow could be formalized, simplified and consistent with the conventional form of diffusion equation. Furthermore, by utilizing the Laplace change and Sethfest inversion changes, the calculated results were obtained and further discussions indicated that transfer mechanisms were influenced by diffusion, adsorption/desorption. The research shows that when the matrix permeability is closed to magnitude of 10^-9D, the matrix flow only occurs near the surfacial matrix; as to the actual production, the central matrix blocks are barely involved in the production; the closer to the surface of matrix, the lower the pressure is and the more obvious the diffusion effect is; the behavior of adsorption/desorption can increase the matrix flow rate significantly and slow down the pressure of horizontal well obviously.

Thermogravimetric Study on Oxygen Adsorption/Desorption Properties of Double Perovskite Structure Oxides REBaCo_2O_(5+δ)(RE= Pr,Gd,Y)

The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere（Δδ/Vmol）in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5＋δ and PrBaCo2O5＋δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.

Characteristics of isothermal adsorption and desorption of aluminum ion to/from humic acids

The adsorption and desorption characteristics of Al^3＋ to/from humic acids at different pH, ionic strength, and temperature were studied by the C-25 glucosan-gel chromatography method. The results showed that the maximum adsorption amount （Qmax） and adsorption constant （k） increased, whereas, the absolute value of standard thermodynamic molar free energy change （ΔGm^0） decreased with the increase of pH at constant ionic strength and temperature. With ionic strength increasing from 0 to 0.15 mol/L, Qmax, and k increased and the absolute value of ΔGm^0 decreased at constant pH and temperature. High temperature was unfavorable for the adsorption reaction, as indicated by the dramatic decrease of Qmax and the absolute value of ΔGm^0 with an increase in temperature. The standard thermodynamic molar free energy change （ΔGm^0） and the standard thermodynamic enthalpy change （ΔHm^0） of the adsorption reaction were both negative, suggesting that adsorption reaction was spontaneous and exothermic. The desorption rate of HA-Al^3＋ complex accelerated with the decrease of pH, and a significant linear relationship could be obtained between pH and the desorption rates of Al^3＋ from humic acids. These results demonstrated that the Al^3＋ adsorption reaction was a ＂biphase＂ reaction, and adsorption occurred at both the interior and exterior adsorption sites of humic acids.

Adsorption and desorption phenomena on thermally annealed multi-walled carbon nanotubes by XANES study

The multi-walled carbon nanotubes(MWCNTs) studied in this work were synthesized by the catalytic chemical vapor deposition(CCVD) process, and were thermally annealed by the hot filament plasma enhanced(HF PE) method at 550℃ for two hours.The x-ray absorption near edge structure(XANES) technique was used to investigate the adsorption and desorption phenomena of the MWCNTs at normal and grazing incidence angles.The adsorbates were found to have different sensitivities to the thermal annealing.The geometry of the incident beam consistently gave information about the adsorption and desorption phenomena.In addition, the adsorption of non-intrinsic potassium quantitatively affected the intrinsic adsorbates and contributed to increase the conductivity of the MWCNTs.The desorption of potassium was almost 70% greater after the thermal annealing.The potassium non-intrinsic adsorbates are from a physisorption mechanism whereas the intrinsic adsorbates result from chemisorption.