Adsorption equilibrium of binary methane/ethane mixtures in BPL activated carbon: isotherms and calorimetric heats of adsorption

The adsorption of pure methane and ethane in BPL activated carbon has been measured at temperatures between 264 and 373 K and at pressures up to 3.3 MPa with a bench-scale high-pressure open-flow apparatus. The same apparatus was used to measure the adsorption of binary methane/ethane mixtures in BPL at 301.4 K and at pressures up to 2.6 MPa. Thermodynamic consistency tests demonstrate that the data are thermodynamically consistent. In contrast to two sets of data previously published, we found that the adsorption of binary methane/ethane in BPL behaves ideally (in the sense of obeying ideal adsorbed solution theory, IAST) throughout the pressure and gas-phase composition range studied. A Tian-Calvet type microcalorimeter was used to measure low-pressure isotherms, the isosteric heats of adsorption of pure methane and ethane in BPL activated carbon, and the individual heats of adsorption in binary mixtures, at 297 K and at pressures up to 100 kPa. The mixture heats of adsorption were consistent with IAST.     

Diffusion of condensable vapors in single adsorbent particles measured via concentration-swing frequency response

A concentration-swing frequency response method is extended to examine mass transfer mechanisms and the concentration dependence of mass transfer rates for adsorption of condensable vapors in single adsorbent particles. The adsorption kinetics of water and hexane in BPL activated carbon and the adsorption of water in silica gel are determined at several different concentrations. The mechanism that best describes the adsorption of water in BPL activated carbon is nanopore diffusion. The diffusivity of water in BPL activated carbon has a clear minimum at approximately P/Po = 0.5, and the concentration dependence of the diffusion data are not described well by the Darken relationship. Both nanopore diffusion and the Glueckauf linear driving force models can be used to describe the diffusion of hexane in BPL activated carbon for the pressure range studied, and the dependence of the diffusivity on concentration can be described approximately using the Darken relationship. However, the diffusion of water in silica gel cannot be described by the nanopore diffusion model and is best characterized by the Glueckauf linear driving force model. The results illustrate the ability of concentration-swing frequency response to accurately determine adsorption rate mechanisms and quantify the complex adsorption kinetics of condensable vapors using small quantities of adsorbent.     

Modelling of solid-liquid adsorption: effects of adsorbent heterogeneity

Effects of adsorbent heterogeneity on the adsorption of cobalt phthalocyanine dye on activated carbon have been studied. Adsorption experiments were carried out by varying the temperature and adsorbent mass in batch adsorbers and, in addition, the adsorbent particle size and fluid flow rate in a continuous stirred tank reactor (CSTR)-type adsorber in order to investigate the equilibrium and the kinetics of adsorption.The Brunauer-Emmett-Teller (BET), Langmuir with uniform distribution (LUD) and Langmuir-Freundlich equations are able to represent the equilibrium data with similar accuracy within the range of measurements. Reasonably large values of the heterogeneity parameter (2.69–2.86) show that the carbon surface is energetically heterogeneous.A mathematical model that describes the adsorption dynamics, including film-, pore- and concentration-dependent surface diffusion on an energetically and structurally heterogeneous adsorbent, is presented here and fitted to the experimental concentration vs. time curves obtained in the continuously stirred tank adsorber.Structural heterogeneity of the carbon, if not accounted for in the kinetic model, can be responsible for the very strong concentration dependence of the surface diffusion coefficient and for the variation in the parameter D_o with particle size and adsorber porosity as shown in this work.     

ADSORPTION ISOTHERMS AND POTENTIAL DISTRIBUTIONS OF NITROGEN ON VARIOUS ACTIVATED CARBONS

The adsorption isotherms of four activated carbons (Norit RB1, Chemviron BPL, Monolit, and Ambersorb-572) have been examined by nitrogen adsorption at 77.5 K. A method for adsorption potential distribution calculation has been proposed based on the adsorption isotherms. This distribution provides information about possible changes in the Gibbs free energy caused by the energetic and geometrical heterogeneities of an activated carbon as well as by the adsorbate-related entropic effects. The general character of the adsorption potential distribution is clearly visible by its simple relation to the micropore and mesopore distribution.     

ADSORPTION ISOTHERMS AND POTENTIAL DISTRIBUTIONS OF NITROGEN ON VARIOUS ACTIVATED CARBONS

1. INTRODUCTION Activated carbon, a kind of microporous materials, is widely used as adsorbents and catalytic supports. The knowledge of their basic sorption and structural characteristics is an important factor that determines or limits their applications. Various modern techniques, such as electron microscopy, small angle X-ray scattering, NMR, and some classical measurements, such as calorimetric measurements, adsorption-desorption of vapors and liquids, have been applied. Classical a…     

Polymer adsorption onto a micro-sphere from optical tweezers electrophoresis

We explore the design and operation of an optical-tweezers electrophoresis apparatus to resolve polymer adsorption dynamics onto a single micro-sphere in a micro-fluidic environment. Our model system represents a broader class of micro-fluidic electrophoresis experiments for biosensing and fundamental colloid and surface science diagnostics. We track the adsorption of 100 kDa poly(ethylene oxide) homopolymer onto a colloidal silica sphere that is optically trapped in a crossed parallel-plate micro-channel. The adsorption dynamics are probed on the ～1 μm particle length scale with ～1 s temporal resolution. Because the particle electrophoretic mobility and channel electro-osmotic flow are exquisitely sensitive to the polymer layer hydrodynamic thickness, particle dynamics can be complicated by polymer adsorption onto the micro-channel walls. Nevertheless, using experiments and a theoretical model of electro-osmotic flow in channels with non-uniform wall ζ-potentials, we show that such influences can be mitigated by adopting a symmetrical flow configuration. The equilibrium hydrodynamic layer thickness of 100 kDa poly(ethylene oxide) on colloidal silica is ～10 nm at polymer concentrations ?10 ppm (weight percent), with the dynamics reflecting polymer solution concentration, flow rate, and polydispersity.     

Equilibrium adsorption data from temperature-programmed desorption experiments

This work describes a novel method that enables the calculation of a series of adsorption isotherms basically from a single Temperature-Programmed Desorption (TPD) experiment. The basic idea is to saturate an adsorbent packed in a fixed bed at a certain feed concentration and temperature and to subsequently increase its temperature linearly with time, while maintaining a constant feed concentration.We measured TPD response curves for carbon dioxide on activated carbon at different heating rates for various combinations of feed concentration, molar flow rate and particle size. Response curves from an axially dispersed plug flow model were fitted to experimental data by adjustment of the Langmuir parameters. Adsorption isotherms calculated with these fitted parameters are in good agreement with adsorption data obtained by other methods over the full temperature range.The influence of heating rate on intraparticle mass transfer resistance is discussed.     

Characteristics of Nonafluorobutyl Methyl Ether (NFE) Adsorption onto Activated Carbon Fibers and Different-Size-Activated Carbon Particles

The characteristics of adsorption of 1,1,1,2,2,3,3,4,4-nonafluorobutyl methyl ether (NFE), a chlorofluorocarbon (CFC) replacement, onto six different activated carbon; preparations (three activated carbon fibers and three different-sized activated carbon particles) were investigated to evaluate the interaction between activated carbon surfaces and NFE. The amount of NFE adsorbed onto the three activated carbon fibers increased with increasing specific surface area and pore volume. The amount of NFE adsorbed onto the three different-sized-activated carbon particles increased with an increase in the particle diameter of the granular activated carbon. The differential heat of the NFE adsorption onto three activated carbon fibers depended on the porosity structure of the activated carbon fibers. The adsorption rate of NFE was also investigated in order to evaluate the efficiency of NFE recovery by the activated carbon surface. The Sameshima equation was used to obtain the isotherms of NFE adsorption onto the activated carbon fibers and different-sized-activated carbon particles. The rate constant k for NFE adsorption onto activated carbon fibers was larger for increased specific surface area and pore volume. The rate of NFE adsorption on activated carbons of three different particle sizes decreased with increasing particle diameter at a low initial pressure. The adsorption isotherms of NFE for the six activated carbons conformed to the Dubinin-Radushkevich equation; the constants BE(0) (the affinity between adsorbate and adsorbent) and W(0) (the adsorption capacity) were calculated. These results indicated that the interaction between the activated carbon and NFE was larger with the smaller specific surface area of the activated carbon fibers and with the smaller particle diameter of the different-sized-activated carbon particles. The degree of packing of NFE in the pores of the activated carbon fibers was greater than that in the pores of the granular activated carbons. Copyright 2000 Academic Press.     

粒径和流速对吸附速率的影响

本文主要考察了吸附剂的粒径大小及动态循环时流速大小对吸附速率的影响，根据膜扩散限制和孔隙扩散限制的理论模型对其影响作了定量描述。     

Adsorption of Safranin-T from wastewater using waste materials- activated carbon and activated rice husks

Textile effluents are major industrial polluters because of high color content, about 15% unfixed dyes and salts. The present paper is aimed to investigate and develop cheap adsorption methods for color removal from wastewater using waste materials activated carbon and activated rice husk-as adsorbents. The method was employed for the removal of Safranin-T and the influence of various factors such as adsorbent dose, adsorbate concentration, particle size, temperature, contact time, and pH was studied. The adsorption of the dye over both the adsorbents was found to follow Langmuir and Freundlich adsorption isotherm models. Based on these models, different useful thermodynamic parameters have been evaluated for both the adsorption processes. The adsorption of Safranin-T over activated carbon and activated rice husks follows first-order kinetics and the rate constants for the adsorption processes decrease with increase in temperature.     

Physical and chemical properties of PAN-derived electrospun activated carbon nanofibers and their potential for use as an adsorbent for toxic industrial chemicals

A recently developed carbon material, electrospun Activated Carbon nanoFiber (ACnF), exhibits strong potential for use as an adsorbent for toxic industrial chemicals (TICs). As-prepared ACnF contains as much as 9.6?wt% nitrogen, creating a basic surface that enhances acid-gas adsorption. ACnF shows 4–20 times greater HCN adsorption capacities and 2–5 times greater SO₂ adsorption capacities in dry nitrogen, compared to commercially available activated carbon fiber cloth (ACFC) and Calgon BPL? granular activated carbon, which are considered here as reference adsorbents. ACnF has 50?% of the micropore volume (0.30?cm³/g) of these reference adsorbents, which limits its adsorption capacity at high concentrations for volatile organic compounds (>500?ppm_v). However, at low concentrations (<500?ppm_v), ACnF has a similar capacity to ACFC and about three times the VOC adsorption capacity of Calgon BPL?. ACnF’s small fiber diameters (0.2–1.5?μm) allow for higher mass transfer coefficients, resulting in adsorption kinetics nearly twice as fast as ACFC and eight times as fast as Calgon BPL?. ACnF drawbacks include hydrophilicity and reduced structural strength. The rapid adsorption kinetics and high capacity for acidic TICs warrant further investigation of ACnF as an adsorbent in respiratory protection and indoor air quality applications.     

Water adsorption with hysteresis effect onto microporous activated carbon fabrics

Understanding the adsorption of water vapor onto activated carbons is important for designing processes to remove dilute contaminants from humid gas streams, such as providing protection against chemical warfare agents (CWAs), or against toxic industrial compounds (TICs) used in a terrorist chemical attack. Water vapor isotherms for Calgon BPL granular activated carbon (GAC), military ASZM-TEDA GAC, electrospun activated carbon nanofibers (ACnF), Calgon Zorflex^™ activated carbon cloth, and Novoloid-based activated carbon fiber cloth (ACFC) are presented. Of particular interest are the ACFC isotherms, which exhibit an unusually high degree of hydrophobicity. The ACFC isotherms also show a correlation between water vapor adsorption hysteresis and the level of activation. Water vapor isotherm models from the literature are compared.     

Porosity characteristics and pore developments of various particle sizes palm kernel shells activated carbon (PKSAC) and its potential applications

The adsorption behaviour and the micro- and mesopore size distributions of commercial palm kernel shell activated carbons (PKSAC) and other commercial activated carbon are characterized. The results showed that PKSAC are predominantly microporous materials, where micropores account 68–79% of total porosity. On the other hand, commercial activated carbons: Norit SX Plus, Calgon 12×40, and Shirasagi “A” activated carbons contained high mesopore fraction ranging from 33 to 52%. The analysis showed that the degree of mesoporosity of PKSAC is increased steadily with the decrease of particle size. This is due to the presence of channels interconnect the smaller pores in the interior of smaller particle size PKSAC. The smaller size PKSAC particle that is highly mesoporous has preformed better on the adsorption of larger molecules such as methylene blue. On the other hand, bigger size PKSAC particle has better performance on the adsorption of smaller adsorbates such as iodine.     

Monte carlo simulation and pore-size distribution analysis of the isosteric heat of adsorption of methane in activated carbon

The isosteric heat of adsorption of methane in an activated carbon adsorbent has been modeled by Monte Carlo simulation, using a pore-size distribution (PSD) to relate simulation results for pores of different sizes to the experimental adsorbent. Excellent fits were obtained between experimental and simulated isosteric heats of adsorption of methane in BPL activated carbon. The PSD was then used to predict the adsorption of methane and ethane in the same carbon adsorbent, with good results. The PSD derived from isosteric heat data was shown to be richer in information than PSDs obtained by the more conventional method of fitting to isotherm data.     

Prediction of high-pressure adsorption equilibrium of supercritical gases using density functional theory

In this paper, we present the results of the prediction of the high-pressure adsorption equilibrium of supercritical gases (Ar, N2, CH4, and CO2) on various activated carbons (BPL, PCB, and Norit R1 extra) at various temperatures using a density-functional-theory-based finite wall thickness (FWT) model. Pore size distribution results of the carbons are taken from our recent previous work,(1,2) using this approach for characterization. To validate the model, isotherms calculated from the density functional theory (DFT) approach are comprehensively verified against those determined by grand canonical Monte Carlo (GCMC) simulation, before the theoretical adsorption isotherms of these investigated carbons calculated by the model are compared with the experimental adsorption measurements of the carbons. We illustrate the accuracy and consistency of the FWT model for the prediction of adsorption isotherms of the all investigated gases. The pore network connectivity problem occurring in the examined carbons is also discussed, and on the basis of the success of the predictions assuming a similar pore size distribution for accessible and inaccessible regions, it is suggested that this is largely related to the disordered nature of the carbon.     

Adsorption of phenol by oil-palm-shell activated carbons

Steam activated carbons from oil-palm shells were prepared and used in the adsorption of phenol. The activated carbon had a well-developed mesopore structure which accounted for 45% of the total pore volume. The BET surface area of the activated carbon was 1183 m²/g and a total pore volume of 0.69 cm³/g using N₂ adsorption at 77 K. The adsorption capacity of the activated carbon for phenol was 319 mg/g of adsorbent at 298 K. The adsorption isotherms could be described by both the Langmuir-Freundlich and the Langmuir equations. The adsorption kinetics consisted of a rapid initial uptake phase, followed by a slow approach to equilibrium. A new multipore model is proposed that takes into account of a concentration dependent surface diffusion coefficient within the particle. This model is an improvement to the traditional branched pore model. The theoretical concentration versus time curve generated by the proposed model fitted the experimental data for phenol adsorption reasonably well. Phenol adsorption tests were also carried out on a commercial activated carbon known as Calgon OLC Plus 12×30 and the agreement between these adsorption data and the proposed model was equally good.     

Elution and frontal dynamics of adsorption of organic substances on activated carbon

The elution dynamics of adsorption on activated carbon was studied at various carrier-gas flow rates for a series of organic substances. With the help of the model of the equilibrium adsorption layer that uses the adsorption isotherm described by the theory of volume filling of micropores the outlet curves for the elution and frontal dynamics of adsorption can be adequately predicted. The effective kinetic coefficient and the parameters of the adsorption isotherm were found to be constant for the elution curves calculated both in the elution and frontal regimes of the adsorption dynamics over the whole range of concentrations studied. The effective kinetic coefficient in the mathematical model employed for the systems with microporous adsorbents is independent in fact of the nature of an adsorptive and is mainly determined by the parameters of porous structure of activated carbon and the experimental conditions of a dynamic run.     

热重分析技术测定二苯并呋喃在活性炭上的吸附相平衡

以吸附动力学为基础,建立了热重分析技术测定难挥发性有机物吸附等温线的方法.通过热重分析实验测定了不同升温速率下二苯并呋喃从Norit RB1和Chemviton BPL活性炭上脱附速率曲线,及对应的脱附峰温度.运用所提出的方法,对二苯并呋喃在Norit RB1和ChemvironBPL活性炭上的Langmuir吸附等温线方程进行了估算.估算结果与静态吸附实验测定结果相比,误差不超过10%.     

Porous structure of activated carbons and tert-butylbenzene breakthrough dynamics

The structural and adsorptive characteristics of six activated carbons were studied by means of nitrogen and benzene adsorption and water desorption. Tert-butylbenzene (TBB) breakthrough dynamics was analyzed by using several integral equations solved with a regularization/singular-value decomposition procedure. TBB interaction with texturally different activated carbons with the presence of preadsorbed or adsorbed water under dynamic conditions was illustrated by the breakthrough plots handled with several models. The influence of the type of activated carbons, their pore size distributions, water vapor, and TBB flow rate on the breakthrough times (tb) and the dynamic capacity of the carbon beds has been explored with better results for a carbon sample possessing a maximal contribution of mesopores at half-width x>1.5 nm among the carbons studied (which also appears on benzene adsorption) and a major contribution of microporocity as VDS/Vp approximately 0.88 and SK/SBET approximately 0.15. Another adsorbent, which is characterized by a similar total porosity but a larger micropore volume, a smaller contribution of mesopores (SK/SBET approximately 0.08), greater total and miroporous specific surface areas, and greater intensity of the pore size distribution at x<1.5 nm, shows the second result in dynamic TBB retention.     

流动注射分光光度法研究离子强度对活性炭吸附阴离子染料的影响

利用流动注射分光光度法技术，考察了不同离子强度（NaCl)下，在水溶液中表面带负电的活性炭分别吸附3种阴离子染料的动力学行为．利用固-液相互作用方程，求取了活性炭-染料相互作用能．比较了无机盐中阳离子的种类对吸附影响的差异．结果表明：对于3种阴离子染料，离子强度的增大都起到加速吸附的作用：表现吸附速率常数、活性炭-染料相互作用能与离子强度三者之间存在密切的内在联系：在相同离子强度下，二价阳离子对吸附的加速作用要比一价阳离子的显著，但在同价阳离子之间这种作用的差别较小．