CO_2 isothermal adsorption models of coal in the Haishiwan Coalfield

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.

Adsorption of methane onto mudstones under supercritical conditions: Mechanisms, physical properties and thermodynamic parameters

Since the mechanisms of methane-mudstone interactions are important for estimating shale gas reserves,methane adsorption under supercritical conditions of 30 MPa pressure and 303.15,333.15,363.15 K temperatures was studied to measure the excess methane adsorption in two mudstone samples from Yanchang Formation,Ordos Basin.Excess adsorption features inflection points where the amount of adsorbed gas changes from increasing to decreasing concentrations.Three methods(fixed,slope,and freely fitted density)were applied to calculate the adsorbed-phase density(rad),which was then used to fit the measured excess adsorption.Two criteria,the goodness-of-fit and whether the fitting can obtain reasonable absolute adsorption,were applied to determine the most accurate model.Results indicated that the supercritical Dubinin-Radushkevich(SDR)model with freely fitted rad was the most reasonable model.The volume of adsorbed methane at 363.15 K is close to the micropore(d<2 nm)volume of the corresponding mudstone.Considering the actual geological conditions,the adsorbed gas should be predominantly stored in micropores.Thermodynamic parameters reveal that the methane adsorption on mudstone is a physisorption process that is jointly controlled by the heterogeneity of,and interaction forces between the methane molecule and,the rock surface.

Effects of O_(2)adsorption on secondary electron emission properties

The surface adsorption of gas molecules is a key factor limiting the secondary electron yield(SEY)of a material in many areas of applied physics.The influence of O_(2)adsorption on the SEY of metallic Ag is investigated in this work.To account for the particle distribution,we propose a BET theory based on multilayer O_(2)physisorption model.Furthermore,based on the phenomenological model of secondary electron(SE)emission and by taking into account the different scattering processes between electrons and particles in the adsorbed layer,we develop a numerical model of SEY in the adsorbed state using Monte Carlo simulations.The relationships among O_(2)adsorption,adsorption layer thickness,and SEY variation characteristics are then examined through a series of experiments.After 12-h exposure to O_(2),the clean samples increases12%-19%of the maximum value of SEY and 2.3 nm in thickness of the adsorbed layer.Experimental results are also compared with the results from the MC model to determine whether the model is accurate.

CO2-hierarchical activated carbon prepared from coal gasification residue: Adsorption equilibrium, isotherm, kinetic and thermodynamic studies for methylene blue removal

Mineral matter in a residue(RC G)from coal gasification(CG)was removed by two-stage acid leaching.Hierarchical activated carbon(HAC)was prepared by activating RC Gwith CO2.The performance of HAC on removing methylene blue(MB)from an aqueous solution was investigated.HAC was characterized by N2 adsorption–desorption isotherm,Fourier transform infrared spectroscopy,and scanning electron microscopy.The results show that HAC exhibits hierarchical pore structure with high specific surface area(862.76 m2·g-1)and total pore volume(0.684 cm3·g-1),and abundant organic functional groups.The adsorption equilibrium data of MB on HAC are best fitted to the Redlich-Peterson.The kinetic data show that the pseudo-first-order model is more suitable at low MB concentration,while the advantages of the pseudo-second-orderand the Elovich models are more obvious as the concentration increases.According to the thermodynamic parameters,the HAC-MB adsorption process is spontaneous and endothermic.

Modelling and thermodynamic properties of pure CO_(2)and fue gas sorption data on South African coals using Langmuir,Freundlich,Temkin,and extended Langmuir isotherm models

Carbon sequestration in unmineable coal seams has been proposed as one of the most attractive technologies to mitigate carbon dioxide(CO_(2))emissions in which CO_(2)is stored in the microporous structure of the coal matrix in an adsorbed state.The CO_(2)adsorption process is hence considered one of the more efective methodologies in environmental sciences.Thus,adsorption isotherm measurements and modelling are key important scientifc measures required in understanding the adsorption system,mechanism,and process optimization in coalbeds.In this paper,three renowned and reliable adsorption isotherm models were employed including Langmuir,Freundlich,and Temkin for pure CO_(2)adsorption data,and the extended-Langmuir model for multicomponent,such as fue gas mixture-adsorption data as investigated in this research work.Also,signifcant thermodynamics properties including the standard enthalpy change(ΔH°),entropy change(ΔS°),and Gibbs free energy(ΔG°)were assessed using the van’t Hof equation.The statistical evaluation of the goodness-of-ft was done using three(3)statistical data analysis methods including correlation coefcient(R^(2)),standard deviation(σ),and standard error(SE).The Langmuir isotherm model accurately represent the pure CO_(2)adsorption on the coals than Freundlich and Temkin.The extended Langmuir gives best experimental data ft for the fue gas.The thermodynamic evaluations revealed that CO_(2)adsorption on the South African coals is feasible,spontaneous,and exothermic;and the adsorption mechanism is a combined physical and chemical interaction between the adsorbate and the adsorbent.

A NEW MODEL FOR PHYSICAL ADSORPTION ON SOLID SURFACES

The principal assumptions about equivalence and energy distribution of the asdorption sites on solidsurfaces used by Langmuir for deriving the equation of monomolecular adsorption are generalized and anew physical adsorption model is proposed and tested with experimental data published in literature.Themodels of Langmuir,Freundlich,Temkin etc.are only the special cases.Assuming uniform density distributionof adsorption energy,the isotherm equation is given asn=K.1n[1+（bop）1/Mor n=K.1n[1+（boC）1/M]where n is the amount of adsorption per unit weight or area of solid p or C is tbe pressure of gas or the concen-tration of solution respectively.K,bo,M are constants with physical meanings as described in this paper.This equation can be used over wide range to quantitatively represent the five types of physical adsorptionclassified by Brunauer.

Characterization of P-nitrophenol Adsorption Kinetic Properties in Batch and Fixed Bed Adsorbers

P-nitrophenol（PNP） adsorption in batch and fixed bed adsorbers was studied. The homogeneous surface diffusion model（HSDM） based on external mass transfer and intraparticle surface diffusion was used to describe the adsorption kinetics for PNP in stirred batch adsorber at various initial concentrations and activated carbon dosages. The fixed bed model considering both external and internal mass transfer resistances as well as axial dispersion with non-linear isotherm was utilized to predict the fixed bed breakthrough curves for PNP adsorption under the conditions of different flow rates and inlet concentrations. The equilibrium parameters and surface diffusivity（Ds） were obtained from separate experiments in batch adsorber. The obtained value of Ds is 4.187×1012 m2/s. The external film mass transfer coefficient（kf） and axial dispersion coefficient（DL） were estimated by the correlations of Goeuret and Wike-Chang. The Biot number determined by HSDM indicated that the adsorption rate of PNP onto activated carbon in stirred batch was controlled by intraparticle diffusion and film mass transfer. A sensitivity analysis was carried out and showed that the fixed bed model calculations were sensitive to Ds and kf, but insensitive to DL. The sensitivity analysis and Biot number both confirm that intraparticle diffusion and film mass transfer are the controlling mass transfer mechanism in fixed bed adsorption system.

Coalbed methane genesis, occurrence and accumulation in China

Coalbed methane （CBM） is an important type of unconventional gas. Commercial development of CBM in America has been very successful since the 1980s. The CBM industry in Australia and Canada has developed rapidly during the last decade. Commercial development of CBM in China started in the 1990s, and has made great progress. The geological theory of CBM in China has achieved great advancement in genesis, occurrence and accumulation. On the aspect of CBM genesis, five CBM genetic types （primary biogenic gas, secondary biogenic gas, thermal degradation gas, pyrolysis gas and mixed gas） are identified by studying the geochemical characteristics of CBM, and a tracing indicator system is established. The discovery of secondary biogenic gas in medium-high rank coal reservoirs has widened the potential of CBM resources. On the aspect of CBM occurrence, the gas adsorption regulation under combined action of temperature and pressure is revealed by conducting adsorption experiments of different coal ranks under varying temperature and pressure conditions. Besides, by applying the adsorption potential theory in CBM research, the adsorption model under combined action of temperature and pressure is established. The new model can predict CBM resources accurately, and overcome the limitation of the traditional Langmuir model which uses just a single factor to describe the adsorption characteristics of deep buried coal. On the aspect of CBM accumulation, it is proposed that there are three evolutionary stages during CBM accumulation, including gas generation and adsorption, unsaturated gas adsorption, gas desorption-diffusion and preservation. Controlled by tectonic evolution, hydrodynamics and sealing conditions, CBM tends to be regionally enriched in synclines. Advances in geological theory of CBM in China can not only improve understanding of natural gas, but also provide new ideas for further exploration of CBM.

Studies on Heavy Metal Pollution in Soil-Plant System:A Review

Heavy metal pollution in soil-plant system is of major environmental concern on a world scale and in China in particular with the rapid development of industry. The heavy metal pollution status in soil-plant system in China, the research progress on the bioavailability of heavy metals (affecting factors, extraction methods, free-ion activity model, adsorption model, multivariate regression model, Q-I relationship, and compound pollution), and soil remediation are reviewed in the paper. Future research and monitoring is also discussed.

Applicable models for multi-component adsorption of dyes:A review

Adsorption is one of the several techniques that has been successfully used for dyes removal.Since most industrial colored effluents contain several components including dyes,having a strong knowledge about the scope of competitive adsorption process is a powerful key to design an appropriate system.This is mainly because of the complexity brought about by the increasing number of parameters needed for process description which complicates not only the process modeling but also the experimental data collection.A multicomponent adsorption model should be based on fundamental soundness,speed,and simplicity of calculation.For such systems,competition will change the adsorbent-adsorbate attractions.Thus,there is major concern to develop an accurate and reliable method to predict dye adsorption behavior in multi-component systems.This article covers topics such as the theory of dyes adsorption in multi-component systems along with applicable models according to the consistent theories presented by researchers.

Quantum Chemical Study of the Leveling Property of Organic Additives for Ni Electroplating

The geometries of the molecules of eight organic additives were optimized and the net charge,E HOMO andE LUMO were obtained using AM method, respectively. The result shows that there is the correlation between the leveling property and the frontier orbital energy levels of these additives, and the adsorption models and leveling mechanics were discussed. The rule between the frontier orbital energy levels and the leveling property is verified by the experiments.

The Synergistic Effect of Quaternary Ammonium Canons on the Corrosion Inhibition of Fe by Inorganic Anions

The synergistic effect of tetrabutylammonium canon(TBA+)or N-hexadecylpyridinium cation(HDP+)and SCN-or I-in 0. 5 mol. L-1 H2SO4 solution on the corrosion inhibition or Armco iron was investigated by potentiodynamic polarization and polarization resistance measurements. The results show that the synergistic effect of HDP+ containing v-electron and anion is stronger than that of TBA+ and anion.The Joint adsorption models of canon and anion at electrode-solution interface are related to the structure and property of both ions by analyzing the desorption behaviours of both ions when the electrode is polarized anodically.

Investigation on the mechanism of adsorption and desorption behavior in cerium ions modified Y-type zeolite and improved hydrocarbons conversion

Different types of Y zeolites（HY, USY and Na Y） containing various amounts of cerium（Ce） were prepared with the method of liquid ion exchange and characterized by X-ray diffraction（XRD）, intelligent gravimetric analyzer（IGA）, and a molecular simulation technology（grand canonical Monte Carlo simulation, GCMC）. A novel calculation method of desorption index（DI） was proposed and the influence of cerium cationic species on the processes of adsorption-desorption of hydrocarbon molecules（n-octane） on the cerium modified Y zeolites（Ce Y） was studied. The results indicated that Ce ion species played a key role in reducing desorption activation energy of n-octane on Y type zeolites, leading to an improvement of the desorption ability of the Ce Y and the regulation of the adsorption state of n-octane from aggregation to decentralization. These findings are essential factors for enhancing the product selectivity of light hydrocarbon component and the catalytic activity of rare earth modified Y zeolites（REY） catalysts in fluid catalytic cracking（FCC） process.

Single and Binary Dye Adsorption of Methylene Blue and Methyl Orange in Alcohol Aqueous Solution via Rice Husk Based Activated Carbon:Kinetics and Equilibrium Studies

The present work was mainly focused on the single and binary adsorption of methylene blue(MB)and methyl orange(MO)from alcohol aqueous solution over rice husk based activated carbon(RHAC).The study of single dye adsorption equilibrium experiments found that the Langmuir adsorption model was consistent with the adsorption behavior of RHAC on MB and MO,indicating that it was a single layer adsorption.The adsorption behavior con-formed to the pscudo-second-order kinetic model.The binary dye adsorption experiments showed that the Lang-muir-Freundlich model could be applied to describe the adsorption behavior of RHAC on MB and MO.Comparation with the single dye system,the adsorption capacity on the binary dye system was larger,and there was"competitive adsorption"and"synergistic adsorption"effects existed.Meanwhile,the pseudo-second-order kinetic model also fit for the binary dye adsorption behavior.

Adsorption of emerging sodium p-perfluorous nonenoxybenzene sulfonate(OBS) onto soils: Kinetics, isotherms and mechanisms

The widespread use of sodium p-perfluorous nonenoxybenzene sulfonate(OBS), a typical alternative to perfluorooctane sulfonate, has resulted in potential threats to the environment, but the adsorption behavior of OBS in soils has not yet been reported. In this study, the adsorption behaviors of OBS on five soils with different physicochemical properties were investigated. The rate of OBS adsorption was fast, and most of the OBS uptake was completed within 12 h. The good model fit of OBS adsorption to the pseudo-second-order and Elovich models indicated the occurrence of chemical adsorption. The adsorption isotherms of OBS on the soils were better described by the Freundlich model than by the Langmuir model, suggesting that the OBS adsorption sites on the soils were heterogeneous. This is possibly associated with various adsorption mechanisms including hydrophobic, π-π, hydrogen bonding, and electrostatic interactions,further confirmed by the good model fit to the D-R isotherm. Adsorption of OBS occurred on the soils, and the adsorption process was spontaneous and endothermic. In addition, the soils were more suitable for OBS adsorption at lower pH values due to the stronger electrostatic adsorption. The OBS adsorption on the soils decreased with the increase of soil depth from 0 to 30 cm. Moreover, the presence of organic matter and ammonia nitrogen in the soils was favorable for OBS adsorption, and these parameters decreased with increasing soil depth, making OBS adsorption less prominent in the deeper soil. This study indicates that OBS is easily enriched in surface soils, and that soil organic matter and ammonia nitrogen significantly affect OBS migration in soil.

Differences in Adsorption of Anionic Surfactant AOT by Calcium Oxalate： Effect of Crystal Size and Crystalline Phase

The adsorption of anionic surfactant sodium diisooctyl sulfosuccinate（AOT） onto calcium oxalate mono- hydrate（COM） and dihydrate（COD） with sizes of 50, 100 nm, 1, 3 and 10 μm was comparatively studied to simulate the interaction between urinary crystallites and urine components. The adsorption quantity of different concentrations of AOT onto COD and COM with different sizes was detected using a UV-Vis spectrophotometer. The crystalline phase transition of COM and COD before and after adsorption was analyzed by X-ray powder diffraction and Fourier transform infrared spectrometry. The zeta potential of the crystal surface after adsorption of different concentrations of AOT was measured using a zeta potential analyzer. The adsorption quantity of AOT on COM and COD with different sizes was ranked in the following order： 50 nm〉100 nm〉1μm〉3 μm〉10 μm. The adsorption quantity of COM was greater than that of COD with the same size because the density of the positive charges on the COM surface was higher than that on COD surface. With the increase of AOT concentration, the adsorption curves of the large-sized COM and COD（3 and 10μm） were S-type, whereas the adsorption curves of the small-sized COM and COD（50 nm, 100 nm and 1μm） were linear. The adsorption capacities of small-sized COM and COD were much greater than those of the 3 and 10μm crystals. On the basis of the above results, we proposed a molecular model to summarize the absorption of AOT onto COM and COD crystals. Small crystals exhibit a large specific surface area and high surface energy. Thus, the adsorption capacities of them are stronger than those of large crystals. Overall, this study implies that small crystals can easily absorb anionic molecules in urine and may easily adhere to a negatively charged cell surface, thereby increasing the severity of cell injury.

Adsorption of carbon dioxide on amine-modified TiO_2 nanotubes

TiO2 nanotubes （TiNT） were prepared by a hydrothermal treatment and modified by three kinds of amines,namely ethylenediamine,polyetherimide and tetraethylenepentamine （TEPA）,to study their CO2 adsorption properties from gas streams.The resultant samples were characterized by X-ray diffraction,transmission electron microscopy,and infrared spectroscopy,as well as low temperature N 2 adsorption.CO2 capture was investigated in a dynamic packed column at 30℃.TEPA-modified TiO2 nanotubes showed the highest adsorption capacity of 167.64 mg/g because it had the highest amino-group content among the three amines.CO2 fixation on TiNT impregnated by TEPA was investigated at 30,50,and 70℃,and the adsorption capacity increased slightly with temperature.Following the adsorption step,the sorbents were regenerated by temperature programmed desorption,and the TiNT-TEPA sample,as CO2 sorbent,was found to be readily regenerated and energy-efficient.The cycle test also revealed that the TiNT-TEPA adsorbent is fairly stable,with only a 5% drop in the adsorption capacity after 10 adsorption/desorption cycles.In addition,the CO2 adsorption behavior was investigated with the deactivation model,and which showed an excellent prediction for the TiNT-TEPA breakthrough curves.

CO_2 adsorption using TiO_2 composite polymeric membranes:A kinetic study

CO2is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO2. Membrane gas separation is a fast growing CO2 capture technique, particularly gas separation by composite membranes. The separation of CO2 by a membrane is not just a process to physically sieve out of CO2 through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO2. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO2 in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO2 through membranes. Pure cellulose acetate（CA） and cellulose acetatetitania nanoparticle（CA-TiO2） composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO2 membrane adsorbed more quantity of CO2 gas as compared to pure CA membrane. The high CO2 adsorption capacity may enhance the diffusion and solubility of CO2 in the CA-TiO2 composite membrane, which results in a better CO2 separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models.According to correlation factor R2, the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion.

Investigation of adsorption behaviors of paraffin waxes on iron, iron oxide, and iron Ⅲ oxide pipeline's internal surfaces using adsorption locator model

Wax deposition in pipelines leads to pressure drop,reduced effective cross-sectional area,and blockages.Although mathematical models and experimental loops were used to model wax precipitation on pipeline surfaces,its prediction at molecular levels is not fully recognized.Molecular dynamics is another powerful approach that can predict wax precipitation at the molecular level.This paper uses molecular dynamics simulations with the adsorption locator model found in Material Studio Software to investigate the adsorption behaviors of Icosane-C20H42,Docosane-C22H46,and Tetracosane-C24H50 paraffin waxes on the Fe,FeO,and Fe2O3 pipeline internal surfaces.Modeling is performed by varying temperature values and validated with experimental data.It was found that as the temperature altered,the adsorption energies,probability energy distribution and adsorption density field on the surfaces also changed;on the other hand,the energetic analysis results showed adsorption energies increase with carbon numbers increase due to its larger surface contacting areas and lower aspect ratio,which resulted in stronger interaction with the surfaces.Further,paraffin waxes showed to adsorb easily on Fe surfaces than oxide surfaces.At temperatures below Wax Appearance Temperature(WAT)on both simulations and experiments showed wax deposition.The lower adsorption energy capacity observed on the Fe2O3 pipeline surface confirms it's vitality and suitability for crude oil transportation pipelines surface lining material.

Selective removal of phenol by spherical particles of α-,β- and γ-cyclodextrin polymers： kinetics and isothermal equilibrium

Spherical particles of α-,β- and γ-cyclodextrin （CD） polymers to efficiently remove phenol from waste water were prepared by reverse suspension polymerization with epichlorohydrin as crosslinker in liquid paraffin. By controlling the amounts of crosslinker and water, well- defined spherical polymer particles with controllable size were obtained. Due to the selective inclusion associations between CD groups and phenol, these CD spherical polymer particles were demonstrated to be ideal candidates for removal of phenol. Among them β-CD polymer particles showed the best performance. The kinetics and isothermal equilibrium models were used to fit the experimental data of phenol removal from aqueous solution using these CD polymer particles. It was found that the kinetics followed the Ho and Mckay equation, suggesting that the adsorption process of phenol was controlled by diffusion and the host-guest interaction between CD and phenol. Equilibrium isothermal data can be well fitted by the Freundlich equation. The negative free energy change indicated the spontaneous nature of adsorption of phenol by α-,β- and γ-CD spherical polymer particles, while the lowest free energy for β-CD polymer reflected its best adsorption ability, compared to α- and γ- CD polymer particles.