Application of kinetic investigations for interpretation ofn-hexane and benzene adsorption on active carbon

Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.

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Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle

Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.

     

Removal of 2.4-dichloro phenoxyacetic acid from aqueous solution by adsorption on activated carbon. A kinetic study

The sorption of 2.4-dichloro phenoxyacetic acid (2.4-D) on two different activated carbons was determined using the batch equilibration technique. The calculated slopes of the Freundlich sorption isotherms were significantly less than 1. The (K) values were higher for the activated carbon which has the higher specific surface, and increased with NaCl concentration. The rate of attaining equilibrium of 2.4-D increased with a decrease in absorbent concentration. Dynamic modelling of the adsorption showed that a first order reversible kinetic model was followed for the adsorption process. The overall rate constant K′, the adsorption rate K₁, the desorption rate constant K₂, and the equilibrium constant K_c for the adsorption process were calculated.     

The adsorption of dyestuffs from aqueous solutions using the activated carbon adsorption model to determine breakthrough curves

A series of breakthrough curves for the adsorption of Deorlene Yellow and Telon Blue on carbon have been used to test a kinetic model. The model is based on the unreacted core theory and assumes resistances due to external mass transfer and pore diffusion, and irreversible adsorption. The experimental and theoretical data are well correlated by the model at low dye flow rates, but the model was modified at high dye flow rates. The effective diffusivities are 4.0 × 10⁻¹⁰ m² s⁻¹ and 3.0 × 10⁻¹⁰ m² s⁻¹ for Deorlene Yellow and Telon Blue respectively.     

Thermodynamic study of triclosan adsorption from aqueous solutions on activated carbon

The change in the thermodynamic properties of triclosan adsorption on three activated carbons with the different surface chemistry was studied through immersion calorimetry and equilibrium data; the amount adsorbed of triclosan (Q) during calorimetry was determined and correlated with the energy associated with adsorbate–adsorbent interactions in the adsorption process. It was noted that triclosan adsorption capacity decreases with an increase in oxygenated surface groups. For an activated carbon oxidized with HNO₃ (OxAC), the amount adsorbed was 8.50?×?10^?3 mmol g^?1, for a activated carbon without modification (GAC) Q?=?10.3?×?10^?3 mmol g^?1 and for a activated carbon heated at 1073 K (RAC1073) Q?=?11.4?×?10^?3 mmol g^?1. The adsorbed amounts were determined by adjusting the isotherms to the Sips model. For the activated carbon RAC1073, the immersion enthalpy (ΔH_imm) was greater than those of the other two activated carbons due to the formation of interactions with the solvent (ΔH_immOxAC?=?? 27.3 J g^?1?<?ΔH_immGAC?=?? 40.0 J g^?1?<?ΔH_imm RAC1073?=???60.7 J g^?1). The changes in the interaction enthalpy and Gibbs energy are associated with adsorbate–adsorbent interactions and side interactions such as the adsorbate–adsorbate and adsorbate–solvent interactions.

     

Kinetics of adsorption and desorption of Pb(II) in aqueous solution on activated carbon by two-site adsorption model

The adsorption and desorption equilibrium and kinetics of lead ions from aqueous solutions on a granular activated carbon (GAC) were examined. Rapid increase followed by slow increase in Pb(II) amount on the GAC was observed as a function of time for the adsorption, while rapid decrease and consecutive very slow decrease was observed in desorption. Based on the experimental results, a two-site adsorption model was proposed for the adsorption and the desorption of Pb(II) under the study conditions. The Pb(II) adsorption on the GAC was estimated to have simultaneously occurred on the strong and the weak adsorption sites. Conventional Langmuir-type kinetic equations were introduced to quantitatively predict the adsorption and desorption with the two-site model by optimizing the parameters to fit the equilibrium and the kinetic experimental results. The equilibrium and kinetic experimental results could be represented by the equations by using one set of the common Langmuir parameters. Resultant kinetic parameters revealed that the adsorption equilibrium constant was two orders of magnitude greater for strong adsorption site than for weak adsorption site, though the maximum number of weak adsorption site was 1.5 times as great as that of strong adsorption site. The strong adsorption equilibrium constant resulted from a small desorption rate constant for the site. The equations were demonstrated to be applicable for predicting other desorption performances as well.     

Competitive adsorption of aqueous metal ions on an oxidized nanoporous activated carbon

Competitive adsorption is the usual situation in real applications, and it is of critical importance in determining the overall performance of an adsorbent. In this study, the competitive adsorption characteristics of all the combinations of binary mixtures of aqueous metal ion species Ca2+(aq), Cd2+(aq), Pb2+(aq), and Hg2+(aq) on a functionalized activated carbon were investigated. The porous structure of the functionalized active carbon was characterized using N2 (77 K) and CO2 (273 K) adsorption. The surface group characteristics were examined by temperature-programmed desorption, Fourier transform infrared spectroscopy, Raman spectroscopy, acid/base titrations, and measurement of the point of zero charge (pHpzc). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for both single-ion and binary mixtures of these species. Hydrolysis of metal species in solution may affect the adsorption, and this is the case for adsorption of Hg2+(aq) and Pb2+(aq). Competitive adsorption decreases the amounts of individual metal ions adsorbed, but the maximum amounts adsorbed still follow the order Hg2+(aq) > Pb2+(aq) > Cd2+(aq) > Ca2+(aq) obtained for single metal ion adsorption. The adsorption isotherms for single metal ion species were used to develop a model for competitive adsorption in binary mixtures, involving exchange of ions in solution with surface proton sites and adsorbed metal ions, with the species having different accessibilities to the porous structure. The model was validated against the experimental data.     

Investigating the adsorption of 2-mercaptothiazoline on activated carbon from aqueous systems

2-Mercaptothiazoline (2-MT) is widely used as an organic corrosive as well as a diffusion inhibitor due to its high ability to form metal-chelate Schiff base complexes. This study investigated the elimination of 2-MT from aqueous systems with adsorption process to reach the goal of sustainable use of water resources. The Freundlich and Langmuir adsorption isotherms were adopted to examine the adsorption behavior of two types of 2-MT (i.e., 2-MT molecule and 2-MT complex) on activated carbon (AC) Chemviron Filtrasorb 400 (F 400) in three different solutions. The results of adsorption isotherm data showed that the adsorption ability of 2-MT molecule is much higher than that of 2-MT complex, whose ability may be reduced due to the electrostatic repulsion. The good applicability of Langmuir adsorption isotherm to experimental data indicated that the adsorption of 2-MT complexes on F 400 might be limited to a monolayer. Higher ionic strength and lower pH value of the solutions promoted the uptake of 2-MT onto F 400 from the solutions. In addition, not only 2-MT molecule and complex but also Cu(II) can be adsorbed on the surface of F 400, which was demonstrated by energy dispersive analysis of X-ray (EDAX). Effects of the two major interactions, chemical and physical interactions, on the adsorption of 2-MT on F 400 were compared as well in this study.     

A radiotracer study of adsorption on activated carbon cloth from aqueous solution

A study has been made on the effect of pH upon the equilibrium adsorption capacity of triethyl phosphate, dimethyl phosphate and orthophosphate on to activated carbon cloth. It is shown that for molecular phosphates no dependence upon pH exists, whilst the adsorption of ionic phosphates exhibit a strong pH dependence. These adsorption trends may be explained in terms of pKa values, ionic strength and the surface charge of the activated carbon cloth is aqueous solution.     

Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions

The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.     

Fixed-bed adsorption of chlorinated hydrocarbons from multicomponent aqueous solution onto activated carbon: equilibrium column model

The results of studies on the adsorption dynamics of light chlorinated hydrocarbons, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, 1,1-dichloroethene, perchloroethylene and 1,1,2-trichloroethene, from a seven-component solution on to activated carbon are presented. The experimental results were described using the equilibrium model. The application of this model allows to determine the location of the midpoint of the breakthrough profile.     

Electrochemically enhanced adsorption of phenol on activated carbon fibers in basic aqueous solution

Electrosorption isotherms and thermodynamics of phenol on activated carbon fibers (ACFs) in basic solution, as well as the factors (bias potential, initial concentration, and electrolyte) affecting adsorption/electrosorption kinetics, were investigated. The kinetics, which followed the Lagergren adsorption rate law, exhibited a variety of responses depending on bias potential, initial concentration, and electrolyte. The electrosorption isotherms were in agreement with the classical models of Langmuir and Freundlich, but the former gave more satisfactory correlation coefficients. With electrosorption at a bias potential of 700 mV from the basic solution, a nearly 10-fold enhancement of maximum adsorption capacity was achievable. The electrosorption free energy (DeltaG(ads)), enthalpy (DeltaH(ads)), and entropy (DeltaS(ads)) of phenol on the ACFs were calculated from adsorption isotherms at different temperatures. The results indicated that electrosorption of phenol in basic solution was spontaneous and exothermic. Furthermore, it was assessed that electrosorption occurred by dipole-dipole interaction with DeltaH(ads) of -20.14 kJ mol(-1) besides suppositional electrostatic interaction.     

Study on adsorption kinetic of aromatic hydrocarbons onto activated carbon in gaseous flow method

The adsorption behavior of benzene, toluene, o-xylene, m-xylene, and p-xylene onto activated carbon was investigated using the flow method. The removal efficiency of aromatic hydrocarbons in the gaseous phase was estimated based on the adsorption kinetic constants and the saturated amount of aromatic hydrocarbons adsorbed on the activated carbon. The saturated amount of benzene and toluene adsorbed was greater than that of xylene adsorbed because the molecular sizes of benzene and toluene are smaller than that of xylene. The adsorption kinetic constant increased in the order of xylene, toluene, and benzene. Those of the three xylene isomers were similar. These results indicated that the adsorption rate of benzene by the activated carbon was the fastest and the kinetic constant depended upon the different between the boiling point and the melting point and the molecular size of the aromatic hydrocarbons.     

甲烷在活性炭上吸附平衡模型的研究

比较吸附模型分析甲烷在活性炭上吸附平衡的适用性,为吸附式天然气(ANG)的工程应用提供准确的预测模型。基于在温度268.15～338.15 K、压力0～12.5 MPa测试的甲烷在Ajax活性炭上的吸附平衡数据,选择Langmuir、Langmuir-Freundlich和Toth方程,应用非线性回归拟合方程参数后,确定绝对吸附量和甲烷吸附相态,并比较方程在不同压力区域内的预测精度。结果表明,甲烷吸附相密度随平衡温度和压力变化;由绝对吸附量确定的甲烷在Ajax活性炭上的平均等量吸附热为15.72 kJ/mol,小于由过剩吸附量的标绘结果;Langmuir、Langmuir-Freundlich和Toth方程预测结果在0～0.025 MPa的累积相对误差为6.449 8%、7.918 4%和0.910 0%,在1～10 MPa为0.491 1%、0.161 3%和0.369 4%。Toth方程在整个压力范围内的预测结果最为准确,但Langmuir-Freundlich方程在较高压力区域内具有较高的预测精度。     

活性炭自水溶液中吸附酚的热力学与机理研究

研究了水溶液中活性炭分别吸附苯酚、邻甲酚过程热力学与机理, 测定了不同温度下的吸附等温线。结果表明, 常温下稀溶液中, 苯酚以垂直与平伏混杂取向被吸附, 高浓度时则以垂直取向为主。邻甲酚以平伏聚向被吸附且取向几乎不受浓度变化的影响, 但受温度的影响, 55~60℃时, 吸附情况与苯酚相似。体系的热力学与吸附机理关系密切。垂直吸附的熵变较小, 平伏吸附的熵较大。对产生上述现象的原因, 本文进行了分析讨论, 并由此阐明了其它固-液吸附体系中的一些问题。     

甲烷在石墨化热解碳黑和活性炭上的吸附

为研究影响碳基吸附剂吸附超临界温度气体的主要因素,选择石墨化热解碳黑BP280和Ajax活性炭,分析超临界温度高压甲烷在其上的吸附平衡。应用容积法,在压力0~20.5 MPa、温度253 K~313 K测定甲烷的吸附平衡数据,并由等量吸附线标绘和亨利定律常数确定等量吸附热。引入通用吸附等温方程,再由方程的Langmuir标绘确定最大吸附容量,进而通过方程的线性化计算吸附平衡态中甲烷分子的作用能。结果表明,甲烷在两种吸附剂上的最大吸附容量均随温度而变化,并都小于液态甲烷的密度;甲烷在碳黑和活性炭上的等量吸附热分别为11.9 kJ/mol~12.5 kJ/mol和17.5 kJ/mol~22.5 kJ/mol,体现了两种吸附剂不同的表面能量分布;甲烷分子间作用能随吸附量的变化特点反映了超临界温度甲烷以类似于压缩气体状态聚集的特点和吸附剂结构上的差异。碳基吸附剂的比表面积和微孔容积是影响其储存甲烷容量的重要因素。     

Modified langmuir-like model for modeling the adsorption from aqueous solutions by activated carbons

A new equation, a modified Langmuir-like equation (M-LLE), for describing adsorption from solution by activated carbons is proposed for the first time in this work. The M-LLE assumes that there are two types of interactions: (a) specific interactions which are typical, enthalpy-driven interactions and (b) nonspecific interactions driven by the loss of water structuring, upon adsorption (hydrophobic bonding), around the nonpolar parts of the drug. The proposed model was evaluated by studying the adsorption of three drugs: procaine, fluoxetine, and phenobarbital by four different activated carbons under different experimental conditions. As the hydrophobicity of the drug increased, the capacity constant representing the interactions driven by hydrophobic bonding (K(HB), M-LLE equation) increased. Experimental conditions that decrease hydrophobic bonding, such as increased temperature and higher cosolvent concentration, resulted in a decrease in K(HB). Salts that tend to increase water structuring and hydrophobic bonding caused an increase in K(HB). All of these studies support the M-LLE, because they support the notion of hydrophobic-bonding-driven interactions.     

Temperature dependence of herbicide adsorption from aqueous solutions on activated carbon fiber and cloth

Diuron and amitrole adsorption from aqueous solution on an activated carbon fiber and an activated carbon cloth were studied as a function of temperature. Diuron adsorption was greater than that of amitrole and increased with rising temperature, whereas amitrole adsorption decreased when the temperature increased. Endothermicity of diuron adsorption was due to an increase in the planarity and diffusion of diuron molecules with higher temperatures. However, the exothermicity found for amitrole was due to the increase in amitrole solubility and in vibrational energy of adsorbed molecules with higher temperature. External mass transfer resistance was also found to play an important role in diuron adsorption on activated carbon cloth.     

Correlation of fractal pore-size distribution of activated carbon fiber with its adsorption for low concentration benzene vapor

Fractal pore-size distribution K(x) is given based on J(x) function proposed by Jaronic. Activated carbon fibers (ACF) with different surface areas are characterized by using two functions mentioned above. The present work studies the fractal pore-size distribution of ACF and adsorption isotherms of nonpolar benzene vapor on ACF, and thereby reveals the correlation between them.     

Carbon dioxide-methane mixture adsorption on activated carbon

In this work, we report new experimental data of pure and binary adsorption equilibria of carbon dioxide and methane on the activated carbon RB2 at 273 and 298 K. The pressure range studied were 0–3.5 MPa for pure gases and 0–0.1 MPa for mixtures. The combination of the generalized Dubinin model to describe the pure CO₂ and CH₄ isotherms with the IAST (Ideal Adsorbed Solution Theory) for the mixtures provide a method for the calculation of the binary adsorption equilibria. This formulation predicts with acceptable accuracy the binary adsorption data and can easily be integrated in general dynamic simulation of PSA (pressure swing adsorption process) adsorption columns. It involves only three parameters, independent of the temperature, and directly determined with only one adsorption isotherm of CO₂.     

Global non-ideality effects in adsorption of organic substances from dilute aqueous solutions on activated carbon

Summary A method for the quantitative estimation of the global non-ideality of the adsorption of weak organic electrolytes on activated carbon from dilute aqueous solutions is presented. The method is based on the analysis of aGraham plot which reflects the adsorption isotherm deviations from ideality. Averaging these deviations over the whole range of adsorption, one gets a single value representing the global non-ideality of a system. The method also allows to estimate the contributions of heterogeneity and interactions in the adsorbed phase to the global non-ideality effect. The theoretical considerations are illustrated by some model calculations. The usefulness of the method is tested for experimental data of benzoic and salicyclic acid adsorption over a wide range ofpH and concentrations.

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Globaler Effekt der Nicht-Idealität bei der Adsorption organischer Substanzen aus verdünnten wässerigen Lösungen an Aktivkohle

Zusammenfassung Es wird eine Methode zur quantitativen Abschätzung der globalen Nicht-Idealität für die Adsorption schwacher organischer Elektrolyte aus verdünnten wässerigen Lösungen an Aktivkohle vorgestellt. Diese Methode basiert auf der Analyse der bekanntenGraham-Abhängigkeit, die die Abweichung der Adsorptionsisotherme von der Idealität zeigt. Bei Errechnung des Durchschnittwertes dieser Abweichung über den ganzen Asorptionsbereich erhält man einen Wert, der die globale Nicht-Idealität für ein Adsorptionssystem charakterisiert. Die Methode erlaubt auch, den Beitrag der Heterogenität und der Wechselwirkungen in der Adsorptionsphase zum globalen Effekt der Nicht-Idealität abzuschätzen. Die theoretischen Erörterungen werden an Hand von Modellberechnungen illustriert. Die Nutzbarkeit der Methode wurde mit experimentellen Daten der Benzoe- und Salicylsäureadsorption in einem weiten Bereich vonpH und Konzentration getestet.