An Adsorption Kinetic Model for Sulfur Dioxide Adsorption by ZL50 Activated Carbon

A semi-empirical adsorption kinetic model was proposed with the time compensation method to describe the chemisorption of SO2 in flue gas by carbon adsorbents for flue gas purification.The change in adsorption capacity and adsorption rate with time at different water vapor concentrations and different SO2 concentrations was studied.The model was in good agreement with experimental data.The surface reaction was probably the rate controlling step in the early stage for SO2 adsorption by ZL50 activated carbon.The parameters m and n in the nth order adsorption kinetic model were related to the magnitude of the time compensation and adsorption driving force,respectively.The change of parameter n with water vapor concentrations and sulfur dioxide concentrations was studied and some physical implications were given.The sum of square errors was less than 1.0 and the average absolute percentage deviations ranged from 0.5 to 3.2.The kinetic model was compared with other models in the literature.

A New Competitive Adsorption Isothermal Model of Heavy Metals in Soils

A new competitive adsorption isothermal model(CAIM)was developed for the coexistent and competitive binding of heavy metals to the soil surface.This model extended the earlier adsorption isothermal models by considering more than one kind of ion adsorption on the soil surface.It was compared with the Langmuir model using different conditions, and it was found that CAIM,which was suitable for competitive ion adsorption at the soil solid-liquid surface,had more advantages than the Langmuir model.The new competitive adsorption isothermal model was used to fit the data of heavy metal(Zn and Cd)competitive adsorption by a yellow soil at two temperatures.The results showed that CAIM was appropriate for the competitive adsorption of heavy metals on the soil surface at different temperatures.The fitted parameters of CAIM had explicit physical meaning.The model allowed for the calculation of the standard molar Gibbs free energy change,the standard molar enthalpy change,and the standard molar entropy change of the competitive adsorption of the heavy metals,Zn and Cd,by the yellow soil at two temperatures using the thermodynamic equilibrium constants.

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.

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.

Adsorption behavior of carbon dioxide and methane in bituminous coal:A molecular simulation study

The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo(GCMC)simulations were then carried out to investigate the single and binary component adsorption of CO_2 and CH_4with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO_2 adsorption is greater than that of CH_4 adsorption. CO_2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH_4, which can account for the larger adsorption capacity of CO_2 in the bituminous coal model. In the case of binary adsorption of CO_2 and CH_4mixtures, CO_2 exhibits the preferential adsorption compared with CH_4 under the studied conditions. The adsorption selectivity of CO_2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO_2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO_2 decreases gradually with the increase of the bulk CO_2 mole fraction and the depth of CO_2 injection site.

Adsorption Equilibrium of Volatile in Condensed Mode Polyethylene Process

In this paper n-hexane is chosen as typical volatile in condensed mode polymerization process, and the adsorption equilibrium of volatile in polyethylene particles is studied through experiments at different temperatures, pressures and particle diameters. It is found that more adsorbed quantity of volatile at equilibrium can be obtained with lower temperature, higher pressure and smaller particle diameter. Under polymerization conditions, the adsorbed quantity at equilibrium is more strongly affected by temperature than by pressure, and if the diameter distribution of particles is very wide the effect of diameter on the adsorbed quantity must be taken into consideration. With theoretical analyses a model is proposed for calculating the adsorbed quantity of volatile at equilibrium.

A simplified adsorption model for water vapor adsorption on activated carbon

A simplified model was developed to describe the water vapor adsorption on activated carbon. The development of the simplified model was started from the original model proposed by DO and his co-workers. Two different kinds of carbon materials were prepared for water vapor adsorption, and the adsorption experiments were conducted at different temperatures(20-50 °C) and relative humidities(5%-99%) to test the model. It is shown that the amount of adsorbed water vapor in micropore decreases with the temperature increasing, and the water molecules form larger water clusters around the functional group as the temperature is up to a higher value. The simplified model describes reasonably well for all the experimental data. According to the fitted values, the parameters of simplified model were represented by the temperature and then the model was used to calculate the water vapor adsorption amount at 25 °C and 35 °C. The results show that the model can get relatively accurate values to calculate the water vapor adsorption on activated carbon.

Adsorption equilibrium for Z-ligustilide on C18-bonded silica from supercritical carbon dioxide

Adsorption equilibrium is of great importance for the preparative supercritical fluid chromatography(pre-SFC) in defining supercritical adsorption behavior and the industrial amplification.This paper presents adsorption isotherms of Z-ligustilide from supercritical carbon dioxide(SC-CO_2) on C18-bonded silica.Adsorption behavior was studied at 305.15 K,313.15 K and 323.15 K with SC-CO_2 density varying from 0.687 g·cm^(-3) to0.863 g·cm^(-3) with the elution by characteristic points(ECP) method.The adsorption amount of Z-ligustilide from SC-CO_2 on C18-bonded silica decreased with the increasing density of the mobile phase as well as the increasing temperature.Adsorption equilibrium data were fitted by Langmuir and Freundlich isotherm models,and the Langmuir isotherm model performed better for describing the whole adsorption process on the column.The monolayer saturation adsorption capacity of Z-ligustilide is in the range of 3.0 × 10^(-4) mg·cm^(-3) to5.5 × 10^(-4) mg·cm^(-3) with an average value of 4.0 × 10^(-4) mg·cm^(-3).

Adsorption of 2-naphthalenesulfonic acid/sulfuric acid/sulfurous acid from aqueous solution by iron-impregnated weakly basic resin：Equilibrium and model

Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid(NSA), sulfuric acid and sulfurous acid from their solution at 298 K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorption models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute competitive adsorption behavior.

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.

Adsorption Rate Models for Multicomponent Adsorption Systems

Three adsorption rate rnodels are derived for multicomponent adsorption systems under either pore diffusion or surface diffusion control. The linear driving force (LDF) model is obtained by assuming a parabolic intraparticle concentration profile. Models Ⅰ and Ⅱ are obtained from the parabolic concentration layer approximation. Examples are presented to demonstrate the usage and accuracy of these models. It is shown that Model Ⅰ is suitable for batch adsorption calculations and Model Ⅱ provides a good approximation in fixed-bed adsorption pro-cesses while the LDF model should not be used in batch adsorption and may be considered acceptable in fixed-bed adsorption where the parameter Ti is relatively large.

A Model for Anion Electric Adsorption on Variable Charge Soils

A model was established for anion electric adsorption on variable charge surfaces and an equation to describe the relationship of adsorption amount with equalibrium concentration and suspension pH was derived according to the principles of surface reaction between variable charge surface and anions.The adsorption behaviours of nitrate and chloride on variable charge soils were modelled and the results showed that the model could describe the adsorption of nitrate very well.

Adsorption behavior of petroleum asphaltenc Adsorption model

Asphaltene is one of the most heavy components, asphaltene adsorption is a serious problem in oil production and processing. In this paper, the progress in the investigation of asphaltene adsorption from the aspects of adsorption model and adsorption behavior is reviewed. Asphaltene of adsorption model include the Langmuir, Freundlich, Langmuir-Freundlich, Rcdlich-Pctcrson, BET adsorption isothcrm. The adsorption behavior of asphaltene was characterized by a variety of structure-probing methods such as N：-adsorption, X-ray diffraction （XRD）, small-angle X-ray scattering （SAXS） measurements, and FT-IR spectroscopy. To understand better the adsorption progress of petroleum, asphaltene must understand the whole adsorption behavior of asphaltene.

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.

Gas adsorption in shaped zeolitic imidazolate framework-8

Zeolitic imidazolate framework-8(ZIF-8) was prepared through a solve-thermal reaction method and then shaped using different additives. The in fluence of the shaping conditions on the microstructure of the shaped samples was characterized by the XRD, BET, and SEM techniques. The results demonstrate that the compressive strength of the various shaped tablets is greatly increased and capable of meeting the industrial requirements compared to the unshaped ZIF-8 and that the loss rate of speci fic surface areas was maintained at 10% after the addition of 10%(by mass) binder and 10%(by mass) solvent. The adsorption isotherms of CO2, CH4, C3H8, and C3H6 on powdery ZIF-8and the shaped tablets(T-shaped ZIF-8, C-shaped ZIF-8, and N-shaped ZIF-8) were determined through volumetric measurements under different pressures and temperatures(298.2, 323.2, and 348.2 K). The adsorption capacities of the gases on both the ZIF-8 powder and the shaped tablets follow the order C3H6 N C3H8N CO2 N CH4. Furthermore,the results show that the adsorption capacities of the gases on the shaped tablets are lower by approximately 10%–20% than those on the powdery ZIF-8. In fact, the adsorption equilibrium isotherms for CO2, CH4, C3H8, and C3H6 on both powdery and shaped ZIF-8 can be well described by the Langmuir equation.

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.

STOCHASTIC MODEL OF PERIODIC OPERATION PERFORMANCE FOR THE CONTINUOUS COUNTER－CURRENT ADSORPTION PROCESS

A stochastic model is developed to predict the peniodic operation performance ofthe continuous counter-current adsorption process. The model takes into account theeffects of random backmixing of particles, axial dispersion of liquid phase, liquid- film mass transfer, intraparticle diffusion and panticle shape, and can revealclearly the behavior of solid and liquid phase in adsorption process. The simulation results agree with the experimental data rather well.

Adsorption of Naphthol Green B on unburned carbon：2-and3-parameter linear and non-linear equilibrium modelling

The study deals with adsorption of Naphthol Green B on two unburned carbons and the parent coal,from which the UCs have been created in a fluidised-bed power station.Particular attention has been paid to the adsorption equilibrium modelling:experimental data has been analysed using 2-parameter(Langmuir,Freundlich) and3-parameter(Redlich-Peterson) isotherms — both linear and non-linear regressions have been used for the estimation of the isotherm parameters.In the case of both UCs,the Langmuir isotherm model provides the worst fit,whereas 2-parameter Freundlich and 3-parameter Redlich-Peterson models are both good,from which 3-parameter Redlich-Peterson isotherm provides slightly better results(despite the penalty used for the higher number of parameters).In the case of both UCs,the linear regression of Freundlich and Redlich-Peterson models provides good results(comparable with non-linear regressions).Unlike both UCs,the best fit of the experimental data from the adsorption on the coal has been achieved by the Langmuir isotherm model.The results based on the Freundlich or Redlich-Peterson model were(in this case) somewhat worse.

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.