Influence of solvent type on dibenzothiophene adsorption onto activated carbon fiber and granular coconut-shell activated carbon

The adsorption behavior of dibenzothiophene (DBT) on an activated carbon fiber (ACF) and a granular coconut-shell activated carbon (GCSAC) in the solvents n-hexane, n-decane, toluene, and mixture of n-decane and toluene was investigated. The DBT adsorption onto both samples was more active in n-hexane than in n-decane. The lowest DBT adsorption was observed in toluene. Regardless of the type of activated carbons and solvents, all the isotherms fit the Freundlich equation better than the Langmuir equation. At low equilibrium concentrations of <2 mass ppm-S, GCSAC displayed greater capacity for DBT adsorption than did ACF in all the tested solvents. The adsorption kinetics of ACF and GCSAC in all the tested solvents were governed by a pseudo-second-order model.     

Simultaneous adsorption of MIB and NOM onto activated carbon. I. Characterisation of the system and NOM adsorption

The objective of this work was to increase the understanding of the adsorption competition between an odour compound, 2-methylisoborneol, and natural organic material (NOM). Part I describes the characterisation of six commercially available activated carbons, undertaken using nitrogen gas adsorption, surface titrations, and Fourier transform infrared spectroscopy. The natural organic material (NOM) from one raw water and four fractions obtained from an isolation and fractionation procedure undertaken on the same raw water, were characterised using ¹³C NMR, high-performance size exclusion chromatography, UV-visible absorbance and elemental analysis. Simultaneous adsorption of NOM and MIB indicated that the adsorption of the NOM was largely dependent on the pore volume distribution of the activated carbons, and less influenced by the variation in surface chemistry. Larger NOM molecules showed greater relative rates of adsorption where the access to the internal structure of the carbon was restricted by size exclusion, due to the shorter diffusion distances to adsorption sites travelled by the larger molecules. As the concentration of MIB was extremely low compared with that of the NOM in these experiments, no effect of MIB on NOM adsorption was seen. Part II reports the significant effect of the NOM solutions on the adsorption of MIB.     

Comparative study of methylene blue dye adsorption onto activated carbon,graphene oxide,and carbon nanotubes

Three different carbonaceous materials, activated carbon, graphene oxide, and multi-walled carbon nanotubes, were modified by nitric acid and used as adsorbents for the removal of methylene blue dye from aqueous solution. The adsorbents were characterized by N₂ adsorption/desorption isotherms, infrared spectroscopy, particle size, and zeta potential measurements. Batch adsorption experiments were carried out to study the effect of solution pH and contact time on dye adsorption properties. The kinetic studies showed that the adsorption data followed a pseudo second-order kinetic model. The isotherm analysis indicated that the adsorption data can be represented by Langmuir isotherm model. The remarkably strong adsorption capacity normalized by the BET surface area of graphene oxide and carbon nanotubes can be attributed to π–π electron donor acceptor interaction and electrostatic attraction.     

Removal of metal ions from aqueous solution by adsorption onto activated carbon cloths: adsorption competition with organic matter

Activated carbon cloths are recent adsorbents whose adsorption properties are well known for monocomponent solutions of organics or metal ions. However, to treat wastewaters with these materials, their performance has to be determined in multicomponent solution. This work studies adsorption competition between metal ions (Cu²⁺, Pb²⁺) and organic matter (benzoic acid). The first part investigates adsorption equilibrium of monocomponent metal ions solutions and shows the dependence of adsorption capacities on adsorbent porosity and metal ions chemical properties (molecular weight, ionic radius and electronegativity). The influence of pH is also demonstrated. The second part focuses on adsorption competition: (1) between both metal ions (a decrease of adsorption capacities is observed, whose value is related to adsorption kinetics of metal ions); (2) between metal ions and organic matter, in solution or adsorbed onto the activated carbon cloth (a strong influence of pH is shown: when benzoic acid is under benzoate form, in both cases adsorption is increased due to the formation of ligands between adsorbed benzoate ions and metals).     

Adsorption of cationic dye from aqueous solutions by activated carbon

Batch sorption experiments were carried out to remove a cationic dye, methylene blue (MB), from its aqueous solutions using a commercial activated carbon as an adsorbent. Operating variables studied were pH, stirring speed, initial methylene blue concentration and temperature. Adsorption process was attained to the equilibrium within 5 min. The adsorbed amount MB dye on activated carbon slightly changed with increasing pH, and temperature, indicating an endothermic process. The adsorption capacity of methylene blue did not significantly change with increasing stirring speed. The experimental data were analyzed by various isotherm models, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Adsorption measurements showed that the process was very fast and physical in nature. Thermodynamic parameters such as the adsorption entropy (ΔS^o) and adsorption enthalpy (ΔH^o) were also calculated as 0.165 kJ mol⁻¹ K⁻¹ and 49.195 kJ mol⁻¹, respectively. The ΔG^o values varied in range with the mean values showing a gradual increase from −0.256 to −0.780 to −2.764 and −7.914 kJ mol⁻¹ for 293, 313, 323 and 333 K, respectively, in accordance with the positive adsorption entropy value of the adsorption process.     

The importance of finite adsorption kinetics in the sorption of hydrocarbon gases onto a nutshell-derived activated carbon

An activated carbon sample was synthesized from nutshells using a sequential step of carbonization and CO₂ physical activation. Sorption equilibria and kinetics of hydrocarbon gases were measured on this sample at various temperatures and concentrations. The structural heterogeneity of the carbon is characterized by its micropore distribution, which is derived from the analysis of isotherms. The finite kinetics (FK) model [Do, D.D., Wang, K., 1998b. Predictions of adsorption equilibria of non-polar hydrocarbons onto activated carbon. Langmuir 14, 7271-7277; Do, D.D., Wang, K., 1998a. Dual diffusion and finite mass exchange model for adsorption kinetics in activated carbon. A.I.Ch.E. Journal 44, 68.] was employed to describe the sorption kinetics of pure gases and to predict those of binary gas mixtures. The performance of the FK model is compared to that of the HMSD model which assumes the same surface heterogeneity but infinite rates of interchange between the bulk and adsorbed phases. It is demonstrated that the finite kinetics play an important role in the simulation/prediction of desorption kinetics and sorption kinetics of binary gas mixtures.     

Effects of high relative humidity on the dynamic adsorption of dimethyl methylphosphonate (DMMP) on activated carbon

The effects of high relative humidity (RH) on the breakthrough of the nerve agent simulant dimethyl methylphosphonate (DMMP) vapor in beds of ASC-impregnated, activated carbon were investigated. Maximum concentrations of DMMP at room temperature and RH > 60% were found to be lower by more than an order of magnitude than in dry air. The breakthrough time (t_B) of 1.2 × 10⁻⁴ g l⁻¹ DMMP in pre-humidified beds and humid air of RH = 90% was shortened by a factor of 1.6 relative to adsorption in dry beds and dry air. Analysis of the breakthrough curves according to the Wheeler–Jonas model indicated that the high RH lowered the dynamic adsorption capacity (W_E) but had nearly no effect on the critical bed weight (W_C). The reduction of W_E by humidity correlates with the observed displacement of adsorbed water by DMMP. The use of DMMP for testing filter performance is limited to low and intermediate relative humidities. On the other hand, DMMP in dry air can be used to advantage for testing the capacity of new or used respirator filters and for the detection of filter channeling.     

A review of the effects of covapors on adsorption rate coefficients of organic vapors adsorbed onto activated carbon from flowing gases

Published breakthrough time, adsorption rate, and capacity data for components of organic vapor mixtures adsorbed from flows through fixed activated carbon beds have been analyzed. Capacities (as stoichiometric centers of constant pattern breakthrough curves) yielded stoichiometric times τ, which are useful for determining elution orders of mixture components. Where authors did not report calculated adsorption rate coefficients k_v of the Wheeler (or, more general, Reaction Kinetic) breakthrough curve equation, we calculated them from breakthrough times and τ. Ninety-five k_v (in mixture)/k_v (single vapor) ratios at similar vapor concentrations were calculated and averaged for elution order categories. For 43 first-eluting vapors the average ratio (1.07) was statistically no different (standard deviation 0.21) than unity, so that we recommend using the single-vapor k_v for such. Forty-seven second-eluting vapor ratios averaged 0.85 (standard deviation 0.24), also not significantly different from unity; however, other evidence and considerations lead us to recommend using k_v (in mixture)=0.85k_v (single vapor). Five third- and fourth-eluting vapors gave an average of 0.56 (standard deviation 0.16) for a recommended k_v (in mixture)=0.56k_v (single vapor) for such.     

A model for the adsorption of single metal ion solutes in aqueous solution onto activated carbon produced from pecan shells

Adsorption isotherms for activated carbon made from pecan shells have been obtained at 25 °C and an approximate pH of 3 for a number of metal ion solutes. It was found that the Slips and Freundlich equations were satisfactory for explaining the experimental data. The correlation of metal ion adsorption with the solute parameters of metal ion electronegativity and first stability constant of the metal hydroxide was investigated. In the case of most of the metal ions studied, higher electronegativities and stability constants corresponded to the higher adsorption levels of metal ions onto the activated carbon. A correlation was developed that predicts the constants of the Freundlich equation from the selected parameters of the metal ions, and thus can predict the adsorption isotherms at constant pH. The developed correlation gives results with acceptable deviations from experimental data. A procedure is proposed for obtaining similar correlations for different conditions (temperature, pH, carbon type and dosage). The ratio of equivalent metal ions adsorbed to protons released is calculated for the studied metal ions over a range of concentrations. In most cases, particularly at low concentrations, this ratio is close to one, confirming that ion exchange of one proton with one equivalent metal ion is the dominant reaction mechanism.     

Electrochemically enhanced adsorption of aniline on activated carbon fibers

For adsorptive separation processes, the adsorption rate and capacity are two important factors affecting the costs. This study describes the anodic polarization of activated carbon fibers (ACFs), which can enhance the adsorption rate and capacity of aniline. The electrosorption kinetics and the affecting factors (bias potential, electrolyte, and pH) of isotherms for aniline on ACFs were investigated. The adsorption/electrosorption of aniline on ACFs follow pseudo-first-order adsorption kinetics, and the adsorption rate improves with increasing bias potential. The electrosorption isotherms, which exhibit a variety of responses depending on bias potential, electrolyte and pH, follow the two classical models of Langmuir and Freundlich. With electrosorption of aniline from aqueous solution, a two-fold enhancement of adsorption capacity is achievable. The initial and saturated ACFs were characterized using scanning electron micrograph (SEM) and Fourier transform infrared spectroscopy (FT-IR). The SEM micrographs show that the surface of ACFs is not oxidized, which is also verified by cyclic voltammetry results. The FT-IR spectroscopy suggests that the interaction between aniline and ACFs is main weak physisorption instead of chemisorption. These experimental results suggest that the electrochemical polarization of ACFs can effectively improve the adsorption rate and capacity of aniline, which may be due to the enhanced affinity between aniline and ACFs instead of the oxidation on the surface of ACFs or in the solution.     

Effect of pH on adsorption of 2,4-dinitrophenol onto an activated carbon

The adsorption characteristics of 2,4-dinitrophenol from water onto a granular activated carbon, F-400, were studied at pH 4.3, 7 and 10. Adsorption equilibria of 2,4-dinitrophenol on GAC could be represented by Sips equation. Equilibrium capacity increased with decreasing pH. The differences in the rates of adsorption are primarily attributable to the differences in the equilibrium at the various pHs. Intraparticle diffusion was explained by surface diffusion mechanism. An adsorption model based on the linear driving force approximation (LDFA) was used for simulating the adsorption behavior of 2,4-dinitrophenol in a fixed bed adsorber. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

The performance of two adsorption ice making test units using activated carbon and a carbon composite as adsorbents

The available adsorption working pairs applied to adsorption refrigeration system, which utilize activated carbon as adsorbent, are mainly activated carbon-methanol, activated carbon-ammonia, and composite adsorbent-ammonia. The adsorption properties and refrigeration application of these three types of adsorption working pairs are investigated. For the physical adsorbents, consolidated activated carbon showed best heat transfer performance, and activated carbon-methanol showed the best adsorption property because of the large refrigerant amount that can be adsorbed. For the composite adsorbents, the consolidated composite adsorbent with mass ratio of 4:1 between CaCl₂ and activated carbon, showed the highest cooling density when compared to the granular composite adsorbent and to the merely chemical adsorbent. The physical adsorption icemaker that employs consolidated activated carbon-methanol as working pair had the optimum coefficient of refrigeration performance (COP), volume cooling power density (SCP_v) and specific cooling power per kilogram adsorbent (SCP) of 0.125, 9.25 kW/m³ and 32.6 W/kg, respectively. The composite adsorption system that employs the consolidated composite adsorbent had a maximum COP, SCP_v and SCP of 0.35, 52.68 kW/m³ and 493.2 W/kg, respectively, for ice making mode. These results are improved by 1.8, 4.7 and 14 times, respectively, when compared to the results of the physical adsorption icemaker.     

A systematic study and proposed model of the adsorption of binary metal ion solutes in aqueous solution onto activated carbon produced from pecan shells

Adsorption isotherms of a number of binary solute systems have been obtained. The adsorption behavior of these cations in the presence of other metal ions that display strong or intermediate affinities for adsorption sites has been systematically investigated. In this investigation the following factors have been considered: (1) metal ion site competition; (2) charge accumulation near the carbon surface; and (3) speciation of the metal ions. Two multicomponent adsorption models are proposed, and the results are compared to two models presented in the literature. The performance of these models is evaluated by an analysis of error. It is found that models with three interaction parameters generally provide a better fit of the data. In most cases, the proposed two-parameter model gives acceptable results.     

Effect of ZnO loading to activated carbon on Pb(II) adsorption from aqueous solution

The effect of zinc oxide loading to granular activated carbon on Pb(II) adsorption from aqueous solution was studied in comparison with zinc oxide particles and oxidized activated carbon. Cu(II), Cd(II) and nitrobenzene were used as reference adsorbates to investigate the adsorption. The BET surface area and point of zero charge (pH_PZC) in the aqueous solution were measured for the adsorbents. The adsorption isotherms were examined to characterize the adsorption of heavy metals and organic molecules. The heavy metal adsorption was improved by both the zinc oxide loading and the oxidation of activated carbon. In contrast, the adsorption of nitrobenzene was considerably reduced by the oxidation, and slightly decreased by the zinc oxide loading. The zinc oxide loading to the activated carbon was found to be effectively used for the Pb(II) adsorption whereas only a part of surface functional groups was used for the zinc oxide particles and the oxidized activated carbon. From the experimental results, the surface functional groups responsible for the Pb(II) adsorption on the zinc oxide loaded activated carbon were considered to be hydroxyl groups that formed on the oxide, while those on the oxidized activated carbon were considered to be carboxylic groups.     

Nitrogen and hydrogen adsorption of activated carbon fibers modified by fluorination

In this study, activated carbon fibers (ACFs) were surface modified with fluorine and mixed oxygen and fluorine gas to investigate the relationship between changes in surface properties by nitrogen and hydrogen adsorption capacity. The changes in surface properties of modified activated carbon fibers were investigated using X-ray photoelectron spectroscopy (XPS) and compared before and after surface treatment. The specific surface area and pore structures were characterized by the nitrogen adsorption isotherm at liquid nitrogen temperature. Hydrogen adsorption isotherms were obtained at 77 K and 1 bar by a volumetric method. The hydrogen adsorption capacity of fluorinated activated carbon fibers was the smallest of all samples. However, the bulk density in this sample was largest. This result could be explained by virial coefficients. The interaction of hydrogen-surface carbon increased with fluorination as the first virial coefficient. Also, the best fit adsorption model was found to explain the adsorption mechanism using a nonlinear curve fit. According to the goodness-of-fit, the Langmuir–Freundlich isotherm model was in good agreement with experimental data from this study.     

Study to investigate the importance of mass transfer of naproxen sodium onto activated carbon

In the present study, the adsorption of naproxen sodium onto activated carbons (BK4, obtained from white polymeric waste and SK4, obtained from black polymeric waste) was investigated by calculating the parameters of pH, contact time, the concentration of naproxen sodium and the temperature. The adsorption data of naproxen sodium onto activated carbon follows the Langmuir isotherm model and its kinetic processes were described by various kinetic adsorption models. It was determined that the pseudo-second-order model was the best choice among all the available kinetic models to describe the adsorption behaviour of naproxen sodium onto activated carbon. During the present study, the intraparticle diffusion rate constant, the external mass transfer coefficient and the film and pore diffusion coefficient were evaluated at various temperatures. In addition, the thermodynamic parameters of the adsorption of naproxen sodium onto activated carbon were also calculated.