Determination of the micropore volume distribution function of activated carbons by gas adsorption

A new method for the determination of the micropore volume distribution function of activated carbons is presented. It is based on the treatment of pure gas adsorption isotherms by a theoretical model derived from the Hill-de Boer theory. Adsorption data (isotherms and heat curves) for carbon dioxide, ethane and ethylene on activated carbon (F30/470 CHEMVIRON CARBON) have been provided by a thermobalance coupled to a calorimeter (TG-DSC 111 SETARAM) at different temperatures (233, 273, 303 and 323 K) for pressures up to 100 kPa. Adsorption isotherms of carbon dioxide and ethane at 303 and 323 K have been used for the determination of the micropore volume distribution function of the activated carbon of interest. The knowledge of its structure has then allowed the simulation of adsorption isotherms and heats for the same adsorbates at the same temperatures as those experimentally studied. Similar calculations have been conducted for ethylene. Whatever the adsorbate (carbon dioxide and ethane used for the determination of the micropore volume distribution function or ethylene), the mean deviation between experimental and calculated isotherms does not exceed 4% at quasicritical and supercritical temperatures (303 and 323 K). In the same temperature conditions, discrepancies between calculation and experiment reach about 10% for adsorption heats. For both isotherms and heats, large discrepancies appear at low temperature (233 and 273 K). This method allows the determination of the micropore volume distribution function of activated carbons. The validity of the results is insured using several isotherms of several adsorbates and taking into account the calorimetric effect of the phenomenon. That is the reason why this method can also be seen as a new possible model for pure gas adsorption data prediction. This paper also presents a brief summary of the state of the art in this field.     

Equilibrium,kinetics and thermodynamics study of phenols adsorption onto activated carbon obtained from lignocellulosic material (<Emphasis Type="Italic">Eucalyptus Globulus labill</Emphasis> seed)

Activated carbon was prepared from lignocellulosic material (Eucalyptus Globulus labill seed) by chemical activation with ZnCl₂ at two different concentrations (10 and 25 % m/v) named ACS25 and ACS10. The textural characteristics of the activated carbons (ACs) were determined by N₂ adsorption isotherms; these exhibit B.E.T. surface areas of 250 and 300 m² g^?1 for ACS25 and ACS10, respectively, with micropore volume contents of 0.140 and 0.125 cm³ g^?1 in the same order. In addition, the FTIR and Boehm methods were conducted for the chemical characterisation of ACs, where many groups with basic character were found, which favours the adsorption of phenols. The prepared carbonaceous adsorbents were used in the adsorption of wide pollutants monosubstituted phenol derivatives: phenol, 4-nitrophenol and 4-chlorophenol. The effect of temperature on the thermodynamics, kinetic and equilibrium of phenols adsorption on ACs was thoroughly examined. The adsorption kinetics adjusted properly for a pseudo-second-order kinetic model. However, the Elovich model (chemisorption) confirms that phenols adsorption did not occur via the sharing of electrons between the phenolic ring and basal plane of ACs because is not properly adjusted, so the process is given by physisorption. The thermodynamic parameters [i.e. Gibbs free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°)] were also evaluated. The overall adsorption process was exothermic and spontaneous in nature. The values found in the thermodynamic study, confirm that the adsorption process corresponds to a clearly physical process.     

Adsorption of lead(II) from aqueous solution onto several types of activated carbon fibers

In this work, the adsorption of Pb(II) from aqueous solution was investigated on various types of activated carbon fibers (ACFs) manufactured from polyacrylonitrile and phenolic resin. The textural and physicochemical properties of the ACFs were determined by the N₂-BET method and acid-base titration. The experimental adsorption equilibrium data of Pb(II) on the ACFs were obtained in a batch adsorber, and the Langmuir isotherm model better fitted the experimental data. The effects of the type of ACF and precursor of ACF, solution pH and temperature upon the adsorption of Pb(II) on the ACFs were examined in detail. The adsorption capacity was highly dependent upon the precursor of ACF. The Pb(II) adsorption capacity of the ACFs augmented when the solution pH and temperature were increased from 2 to 4 and from 288 to 308 K, respectively. The effect of the pH was attributed to the interactions between the surface of the ACF and Pb²⁺ ions present in the water solution. The Pb(II) adsorption capacity of the ACFs was enhanced by oxidation with HNO₃ solution and the enhancement factor was between 1.1 and 1.4. The reversibility of the adsorption of Pb(II) was investigated by first adsorbing Pb(II) on an ACF and then desorbing the Pb(II). It was noticed that Pb(II) was substantially desorbed from ACF while reducing the solution pH to 2. It was concluded that the Pb(II) was mainly adsorbed on the ACFs by chemisorption, electrostatic interactions and ion exchange.     

STUDY ON THE FACTORS AFFECTING REDUCTION CAPACITIES OF ACTIVATED CARBON FIBERS

1. INTRODUCTION The discharge of effluent containing precious metal ions, which comes from electroplating, mining, smelting, and other industries, not only contaminate the environment where people live, but also cause the waste of natural resources. From…     

Adsorption of oxygen-containing aromatics used in petrochemical,pharmaceutical and food industries by means of lignin based active carbons

The adsorption processes of three aromatic chemicals onto activated carbons (ACs) from aqueous solutions have been studied. Eucalyptus kraft lignin obtained from cellulose industry as a residual biomass has been used to prepare activated carbons by physical activation with CO₂. The influences of the activation time on the surface areas and pore volumes of the ACs were analyzed. The physicochemical properties and the surface chemical structure of the adsorbents have been studied by means of N₂ and CO₂ adsorption, ultimate analysis, XPS, TPD and SEM. XPS and TPD spectra of the ACs have suggested the presence of aromatic rings and carbon-oxygen functional groups in the solid surfaces. The potential use of the ACs for the removal of acetaminophen (paracetamol), salicylic acid and benzoic acid has been investigated at different pH, temperature and contact time. The adsorption equilibrium data have been correlated to Langmuir isotherm model. The thermodynamic study has been developed, the values of ΔH, ΔG, and ΔS have been calculated and they indicated that the processes are endothermic for acetaminophen and exothermic for salicylic and benzoic acids. The analysis of the kinetic experiments showed that the effective diffusivities are low; 10⁻¹² to 10⁻¹¹ cm²/s, and they are the corresponding to intraparticle mass transfer, which appears as the controlling step for the net adsorption processes.     

活性碳纤维吸附的研究Ⅰ-不同工艺制备的活性碳纤维的性能比较

本文比较研究了五种不同工艺制备的活性碳纤维（ACF）的产率、比表面积、孔结构、对有机溶剂蒸汽的吸附和脱附性能、对水溶液中亚甲基兰、苯酚和碘的吸附性能以及它们的热稳定性。实验结果表明，水蒸气活化的ACF比化学活化的ACF有更大的比表面积，但前者产品产率较低而后者很高；不论水蒸气活化还是化学活化的ACF，它们对有机溶剂饱和蒸汽的吸附量都较高，脱附和再吸附的性能也都较好，对水溶液中的苯酚都有较好的吸附能力，但化学活化的ACF对亚甲基兰的吸附量显著小于水蒸气活化的ACF，同时磷酸活化的ACF-P对碘的吸附量也明显偏小；除了用KOH活化的ACF外，其它ACF都有很好的热稳定性。     

Sensitivity of PSA process performance to input variables

Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.     

Adsorption of butane isomers and SF6 on Kureha activated carbon: 1. Equilibrium

Adsorption equilibria of butane isomers and SF6 on Kureha activated carbon were investigated using the volumetric method and the tapered element oscillating microbalance (TEOM) technique. The isotherm data of the butane isomers measured by the TEOM technique are in good agreement with those determined by the volumetric method. Single-component adsorption isotherms are reported at temperatures in the range from 298 to 393 K and at pressures up to 120 kPa. SF6 molecules are mainly adsorbed in the larger micropores, resulting in a lower adsorption capacity. The amount adsorbed for n-butane is slightly higher than that for isobutane in the whole range investigated. This is attributed to the fact that the linear n-butane molecule can adsorb in the smaller micropores. The T6th model appropriately describes the equilibrium data of the butane isomers, while the isotherm data of SF6 can be fitted by the Langmuir model. The isosteric heats associated with adsorption for these three adsorptives show different loading dependences. The present study indicates that the activated carbon can be well characterized by the probe molecules having different molecular sizes.     

On the use of the dual process Langmuir model for predicting unary and binary isosteric heats of adsorption

Analytic expressions for unary and binary isosteric heats of adsorption as a function of the adsorbed phase loading were derived from the dual process Langmuir (DPL) model using the Clausius-Clapeyron equation. Unary isosteric heats of adsorption predicted from these expressions for several adsorbate-adsorbent systems were compared to values in the literature predicted from the well-accepted graphical approach using Toth and unilan models (Adsorption Equilibrium Data Handbook; Prentice Hall: NJ, 1989). Predictions from the DPL model were also compared to rare experimental unary and binary isosteric heats of adsorption in the literature for another adsorbate-adsorbent system. In all cases, very good agreement was obtained, showing that the DPL model can be used in adsorption process modeling for accurately predicting not only ideal and nonideal mixed-gas adsorption equilibria (Langmuir 2011, 27, 4700), but also unary and even binary isosteric heats of adsorption.     

STUDY ON THE FACTORS AFFECTING REDUCTION CAPACITIES OF ACTIVATED CARBON FIBERS

The reduction adsorption of silver diamminonitrate on different kinds of activated carbonfibers (ACF) has been studied in this paper. The effect of different parameters, including adsorptiontemperature, concentrations of activation agents, and activation time on the silver adsorptioncapacities of activated carbon fibers has been investigated The results show that higher temperaturein which the silver complex interacts with ACF. or higher concentration of activation agent, will makehigher reduction adsorption capacities of ACFs. More over, ACFs activated with phosphoric acidhave higher reduction capacities than those activated with zinc chloride or steam.     

Adsorption of phenol on supercritically activated carbon fibres: effect of texture and surface chemistry

The influence of texture and surface chemistry on the phenol adsorption capacity of activated carbon fibres (ACFs) was studied. ACFs were prepared by carbonization of a phenolic textile fibre under nitrogen flow, followed by activation with H(2)O and CO(2) (under atmospheric pressure and supercritical state). The materials were characterised by N(2) and CO(2) adsorption, and by temperature programmed desorption studies. A strong correlation between the amount of adsorbed phenol and the micropore volume has been observed. The relationship between surface oxygen concentration and amount of physisorbed and chemisorbed phenol was assessed, and it was shown that higher amounts of surface oxygen groups decreased the phenol chemisorption capacity of ACFs.     

Neural Network Modeling of Adsorption of Binary Vapour Mixtures

Three neural network models were used for prediction of adsorption equilibria of binary vapour mixtures on an activated carbon. The predictions were compared both with published experimental data and calculated values from the Ideal Adsorption Solution (IAS) model. The neural network was trained using both binary and single component experimental adsorption data. Even for a limited number of data points (about 60) the network models were capable of approximating experimental data very precisely.     

Benzene and toluene adsorption at low concentration on activated carbon fibres

The present study analyses the preparation of activated carbon fibres (ACFs) by the so-called “physical” activation method with steam or carbon dioxide and their application for benzene and toluene adsorption at low concentration (200 ppmv). ACFs have been scarcely studied for the adsorption of these pollutants at low concentration in gaseous phase, despite their interesting features regarding adsorption kinetics, bed pressure drop, possibility of conformation and others. Our results have shown that the preparation method used is suitable to produce ACFs with high adsorption capacities for benzene and toluene at the low concentration used. The fibre morphology of the ACFs does not enhance their performance, which results to be similar to other non-fibrous activated carbons such as granular, pellets and powders. Such good performance of the ACFs, leading to benzene and toluene adsorption capacities as large as 31 g benzene/100 g ACF or 53 g toluene/100 g ACF, can be explained due to their large volume of narrow micropores (<0.7 nm) developed upon activation and their low content in surface oxygen groups. Our results have also shown very good agreement between the adsorption results derived from dynamic adsorption experiments and from adsorption isotherms. As the relative pressure of the organic compound increases the corresponding fraction of narrow micropore volumes filled by benzene and toluene increases. For a given low and comparable relative pressure, toluene always occupies a larger fraction of narrow micropores than benzene.     

Studies on pore structures and surface functional groups of pitch-based activated carbon fibers

The present study concerns the physical activation and chemical oxidation of pitch-based activated carbon fibers (ACFs) as ways to improve the adsorption properties. The surface oxides of the ACFs studied were determined by Boehm's titration and the pore structures were studied by the BET method with N(2)/77 K adsorption. Also, the adsorption properties of the ACFs were investigated with chromium ion adsorption by different adsorption models. As a result, it was observed that carboxyl groups were largely created after nitric acid treatment on ACFs. The affinity for chromium ions increases with increasing specific surface area, micropore volume, and surface functionalities of ACFs as the activation time increases.     

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.     

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.     

Influence of anodic treatment on heavy metal ion removal by activated carbon fibers

In this work, the effect of electrochemical oxidation treatment on activated carbon fibers (ACFs) was studied in the context of Cr(VI), Cu(II), and Ni(II) adsorption behavior. Ten weight percent phosphoric acid (A-ACFs) and ammonia (B-ACFs) were used for acidic and basic electrolytes, respectively. Surface properties of ACFs were determined by X-ray photoelectron spectroscopy (XPS). The specific surface area and the pore structure were evaluated from nitrogen adsorption data at 77 K. As a result, the electrochemical oxidation treatment led to an increase in the amount of oxygen-containing functional groups. Also, the adsorption capacity of the electrochemically oxidized ACFs was improved in the order B-ACFs > A-ACFs > untreated-ACFs, in spite of a decrease in specific surface area which resulted from pore blocking by functional groups and pore destruction by acidic electrolyte. It was clearly found that the heavy metal ions were largely influenced by the functional groups on the ACF surfaces.     

Mechanism of adsorption of different humic acid fractions on mesoporous activated carbons with basic surface characteristics

The effects of the humic acid (HA) nature and the activated carbon (AC) surface chemistry on the effectiveness of HA removal were investigated. Brown (BHA) and gray (GHA) humic acid fractions of different structure and physicochemical properties were tested in the adsorption process using mesoporous ACs. The modification of chemical structure and surface properties of AC was achieved by ammonization (AC/N) and hydrogen treatment (AC/H). Both approaches led to a decrease in the oxygen content followed by an increase in the carbon basicity, maintaining the porous texture of AC nearly unaltered. Over twice higher removal degree of BHA and GHA was observed for the modified ACs. The kinetics of adsorption of HA fractions have been discussed using the pseudo-second-order model and the intraparticle diffusion model. All ACs showed a higher adsorption capacity toward BHA compared to GHA, which is mainly attributed to the lower molecular weight of BHA. The shape of the equilibrium isotherms indicates a strong competition between water and HA molecules for adsorption sites of the carbon surface.     

Adsorption of dyes on activated carbon and graphitic thermal carbon black

The adsorption of a basic dye (Methylene Blue; MB) and an acidic dye (Acid Orange; AO) has been studied on three activated carbons (ACs; FAS, SKD, and BAU) significantly differing in their porous structures and surface concentrations of ion-exchange groups and on graphitic thermal carbon black (GTCB). The effective specific surface area of FAS, SKD, and BAU determined by dye adsorption is, respectively, 60, 50, and 40% of the BET nitrogen adsorption surface area. The MB uptake on ACs and GTCB increases with rising pH, while the AO uptake decreases. Addition of an electrolyte (0.3 M NaCl) virtually does not effect the adsorption of dyes on ACs and GTCB. It is suggested that hydrophobic interactions, and not ionic ones, are the major contributors to the adsorption of dyes on ACs.