Using Different Co-Adjuvant Activating Agents to Improve Activated Carbon Adsorption Capacities

Activated carbon (AC) has proved to be an effective adsorbent for the removal of an assortment of organic and inorganic pollutants from aqueous or gaseous media. However, the pursuit for more effective and cheaper AC is still very active and a diversity of textural and chemical treatments are described as a way to expand their applications. It is well known that the surface area and surface chemistry of AC strongly affect their adsorption capacity [1-3]. In particular, an increase in the nitrogen content has been related to an increase of the basic character and also to the development of the porous structure. In most published work this was achieved through an AC post treatment, including either a reaction with nitrogen containing reagents, such as ammonia, nitric acid, or a diversity of amines. However, the AC prepared directly from a nitrogen rich precursor through a physical or chemical activation is referred to as presenting the best characteristics, namely high nitrogen content, high basic character, low nitrogen leaching and also a good thermal stability [4]. To improve the AC adsorption capacities for acidic pesticide removal from the aqueous phase, we intend to improve the porous structure and introduce nitrogenated groups directly into the AC matrix, using different co-adjuvant activating agents as a nitrogen source, by chemical activation, with potassium hydroxide, of cork or poly(ethyleneterephthalate) (PET) precursors.

Solvent regeneration of activated carbon mixed-matrix membranes for the removal of micropollutants from wastewater

The constantly increasing demand of clean water has become challenging to deal with over the past years, water being an ever more precious resource. In recent times, the existing wastewater treatments had to be integrated with new steps, due to the detection of so-called organic micropollutants (OMPs). These compounds have been shown to adversely affect the environment and possibly human health, even when found in very low concentrations. In order to remove OMPs from wastewater, one possible technique is a hybrid process combining filtration and adsorption. In this work, polyethersulfone multi-channel mixed-matrix membranes with embedded powdered activated carbon (PAC) were tested to investigate the membrane’s adsorption and desorption performance. Micropollutants retention was analyzed using the pharmaceutical compounds diclofenac (DCF), paracetamol (PARA) and carbamazepine (CBZ) in filtration mode, combining the PAC adsorption process with the membrane’s ultrafiltration. Desorption performance was studied through solvent regeneration, using seven different solvents: pure water, pure ethanol, mixture of ethanol and water in different concentration, sodium hydroxide and a mixture of ethanol and sodium hydroxide. Regeneration experiments were carried out in forward-flushing. At first regeneration efficiency was investigated using a single-solute solution (diclofenac in water). The mixture Ethanol/Water (50:50) was found to be the most efficient with long-term retention of 59% after one desorption cycle. It was, therefore, later tested on a membrane previously loaded with a multi-solute solution. Three desorption cycles were performed after which, retention (after 30 min) reached values of 87% for PARA and 72% for CBZ and 55% for DCF, which indicates decent regenerability. A morphological analysis on the membranes confirmed that, in any case, the regeneration cycles did not affect either the membranes’ structure, or the content and distribution of PAC in the matrix.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Montmorillonite/carbon nanocomposites prepared from sucrose for catalytic applications

Sucrose was used to prepare montmorillonite/carbon nanocomposites by calcination in a reduced atmosphere. The aim was to investigate the changes derived from varying the clay and sucrose content in the resulting material and to change the adsorption properties to evaluate its potential to be used in catalytic applications. X-ray diffraction patterns revealed the formation of an intercalated nanostructure composed of carbon-filled clay mineral layers, which was confirmed by the Fourier transform infrared spectra and thermogravimetry curves. Differences in composition and texture surface were detected by scanning electron microscopy images and were supported by viscosity measurements. These measurements were helpful in understanding why the sample prepared with the highest sucrose content presented the lowest gasoline and methylene blue adsorption results and why the highest adsorption properties were attributed to the sample with the highest clay content. Moreover, BET and BJH studies allowed understanding oleic acid catalytic conversion. Finally, a water flux simulation test was performed to determine the mechanical resistance in comparison to an activated carbon. It was found that the nanocomposites were more resistant, supporting their use in catalytic applications for a longer period of time. (C) 2011 Elsevier B.V. All rights reserved.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition

Coating anatase TiO2 onto three different particle supports, activated carbon (AC), gamma -alumina (Al2O3) and silica gel (SiO2), by chemical vapor deposition (CVD) was studied. The effect of the CVD synthesis conditions on the loading rate of anatase TiO2 was investigated. It was found that introducing water vapor during CVD or adsorbing water before CVD was crucial to obtain anatase TiO2 on the surface of the particle supports. The evaporation temperature of precursor, deposition temperature in the reactor, flow rate of carrier gas, and the length of coating time were also important parameters to obtain more uniform and repeatable TiO2 coating. High inflow precursor concentration, high CVD reactor temperature and long coating time tended to cause block problem. Coating TiO2 onto small particles by CVD involved both chemical vapor deposition and particle deposition. It was believed that the latter was the reason for the block problem. In addition, the mechanism of CVD process in this study included two parts, pyrolysis and hydrolysis, and one of them was dominant in the CVD process under different synthesis route. Among the three types of materials, silica gel, with higher surface hydroxyl groups and macropore surface area, was found to be the most efficient support in terms of both anatase TiO2 coating and photocatalytic reaction. (C) 2001 Elsevier Science B.V. All rights reserved.

Modeling volatile organic compounds (voc`s) adsorption onto cup-stacked carbon nanotubes (cscnt) using the linear driving force model

Modeling volatile organic compounds (voc`s) adsorption onto cup-stacked carbon nanotubes (cscnt) using the linear driving force model. Volatile organic compounds (VOC`s) are an important category of air pollutants and adsorption has been employed in the treatment (or simply concentration) of these compounds. The current study used an ordinary analytical methodology to evaluate the properties of a cup-stacked nanotube (CSCNT), a stacking morphology of truncated conical graphene, with large amounts of open edges on the outer surface and empty central channels. This work used a Carbotrap bearing a cup-stacked structure (composite); for comparison, Carbotrap was used as reference (without the nanotube). The retention and saturation capacities of both adsorbents to each concentration used (1, 5, 20 and 35 ppm of toluene and phenol) were evaluated. The composite performance was greater than Carbotrap; the saturation capacities for the composite was 67% higher than Carbotrap (average values). The Langmuir isotherm model was used to fit equilibrium data for both adsorbents, and a linear driving force model (LDF) was used to quantify intraparticle adsorption kinetics. LDF was suitable to describe the curves.

The use of liquid phase adsorption isotherms for characterization of activated carbons

The characterization of three commercial activated carbons was carried out using the adsorption of various compounds in the aqueous phase. For this purpose the generalized adsorption isotherm was employed, and a modification of the Dubinin-Radushkevich pore filling model, incorporating repulsive contributions to the pore potential as well as bulk liquid phase nonideality, was used as the local isotherm. Eight different flavor compounds were used as adsorbates, and the isotherms were jointly fitted to yield a common pore size distribution for each carbon. The bulk liquid phase nonideality was incorporated through the UNIFAC activity coefficient model, and the repulsive contribution to the pore potential was incorporated through the Steele 10-4-3 potential model. The mean micropore network coordination number for each carbon was also determined from the fitted saturation capacity based on percolation theory. Good agreement between the model and the experimental data was observed. In addition, excellent agreement between the bimodal gamma pore size distribution and density functional theory-cum-regularization-based pore size distribution obtained by argon adsorption was also observed, supporting the validity of the model. The results show that liquid phase adsorption, using adsorptive molecules of different sizes, can be an effective means of characterizing the pore size distribution as well as connectivity. Alternately, if the carbon pore size distribution is independently known, the method can be used to measure critical molecular sizes. (C) 2001 Elsevier Science.

Characterization of activated carbons using liquid phase adsorption

A modification of the Dubinin-Radushkevich pore filling model by incorporation of the repulsive contribution to the pore potential, and of bulk non-ideality, is proposed in this paper for characterization of activated carbon using liquid phase adsorption. For this purpose experiments have been performed using ethyl propionate, ethyl butyrate, and ethyl isovalerate as adsorbates and the microporous-mesoporous activated carbons Filtrasorb 400, Norit ROW 0.8 and Norit ROX 0.8 as adsorbents. The repulsive contribution to the pore potential is incorporated through a Lennard-Jones intermolecular potential model, and the bulk-liquid phase non-ideality through the UNIFAC activity coefficient model. For the characterization of activated carbons, the generalized adsorption isotherm is utilized with a bimodal gamma function as the pore size distribution function. It is found that the model can represent the experimental data very well, and significantly better than when the classical energy-size relationship is used, or when bulk non-ideality is neglected. Excellent agreement between the bimodal gamma pore size distribution and DFT-cum-regularization based pore size distribution is also observed, supporting the validity of the proposed model. (C) 2001 Elsevier Science Ltd. All rights reserved.

Characterization of micro-mesoporous carbon media

A simple method to characterize the micro and mesoporous carbon media is discussed. In this method, the overall adsorption quantity is the sum of capacities of all pores (slit shape is assumed), in each of which the process of adsorption occurs in two sequential steps: the multi-layering followed by pore filling steps. The critical factor in these two steps is the enhancement of the pressure of occluded 'free' molecules in the pore as well as the enhancement of the adsorption layer thickness. Both of these enhancements are due to the overlapping of the potential fields contributed by the two opposite walls. The classical BET and modified Kelvin equations are assumed to be applicable for the two steps mentioned above, with the allowance for the enhanced pore pressure, the enhanced adsorption energy and the enhanced BET constant,all of which vary with pore width. The method is then applied to data of many carbon samples of different sources to derive their respective pore size distributions, which are compared with those obtained from DFT analysis. Similar pore size distributions (PSDs) are observed although our method gives sharper distribution. Furthermore, we use our theory to analyze adsorption data of nitrogen at 77 K and that of benzene at 303 K (ambient temperature). The PSDs derived from these two different probe molecules are similar, with some small differences that could be attributed to the molecular properties, such as the collision diameter. Permeation characteristics of sub-critical fluids are also discussed in this paper. (C) 2001 Elsevier Science B.V. All rights reserved.

Characterisation of pore structure of carbon adsorbents using regularisation procedure

The constrained regularisation procedure was applied to compute the pore size distributions (PSDs, f(x)) for a variety of activated carbons using overall adsorption equation based on the combination of the Kelvin equation and the statistical adsorbed film thickness. The impact of the boundary values of relative nitrogen pressure p/p(0) was analysed on the basis of the corresponding alterations in the PSDs. Changes in microporosity and mesoporosity of activated carbons can be described adequately only when the range of p/p(0) is as wide as possible, as at a high initial p/p(0) value, the f(x) curves can be broadened with shifted maxima especially for micropores and narrow mesopores. Comparative analysis of the PSDs and the adsorption potential, adsorption energy and fractal dimension distributions gives useful information on the complete description of the adsorbent characteristics. (C) 2001 Elsevier Science B.V. All rights reserved.

Vacancy solution theory for binary adsorption equilibria in heterogeneous carbon

A heterogeneous modified vacancy solution model of adsorption developed is evaluated. The new model considers the adsorption process through a mass-action law and is thermodynamically consistent, while maintaining the simplicity in calculation of multicomponent adsorption equilibria, as in the original vacancy solution theory. It incorporates the adsorbent heterogeneity through a pore-width-related potential energy, represented by Steele's 10-4-3 potential expression. The experimental data of various hydrocarbons, CO2 and SO2 on four different activated carbons - Ajax, Norit, Nuxit, and BPL - at multiple temperatures over a wide range of pressures were studied by the heterogeneous modified VST model to obtain the isotherm parameters and micropore-size distribution of carbons. The model successfully correlates the single-component adsorption equilibrium data for all compounds studied on various carbons. The fitting results for the vacancy occupancy parameter are consistent with the pressure change on different carbons, and the effect of pore heterogeneity is important in adsorption at elevated pressure. It predicts binary adsorption equilibria better than the IAST scheme, reflecting the significance of molecular size nonideality.

Adsorption in slit-like pores of activated carbons: Improvement of the Horvath and Kawazoe method

Anew thermodynamic approach has been developed in this paper to analyze adsorption in slitlike pores. The equilibrium is described by two thermodynamic conditions: the Helmholtz free energy must be minimal, and the grand potential functional at that minimum must be negative. This approach has led to local isotherms that describe adsorption in the form of a single layer or two layers near the pore walls. In narrow pores local isotherms have one step that could be either very sharp but continuous or discontinuous benchlike for a definite range of pore width. The latter reflects a so-called 0 --> 1 monolayer transition. In relatively wide pores, local isotherms have two steps, of which the first step corresponds to the appearance of two layers near the pore walls, while the second step corresponds to the filling of the space between these layers. All features of local isotherms are in agreement with the results obtained from the density functional theory and Monte Carlo simulations. The approach is used for determining pore size distributions of carbon materials. We illustrate this with the benzene adsorption data on activated carbon at 20, 50, and 80 degreesC, argon adsorption on activated carbon Norit ROX at 87.3 K, and nitrogen adsorption on activated carbon Norit R1 at 77.3 K.

Surface diffusion of strong adsorbing vapours on porous carbon

Surface diffusion of strongly adsorbing hydrocarbon vapours on activated carbon was measured by using a constant molar flow method (D.D. Do, Dynamics of a semi-batch adsorber with constant molar supply rate: a method for studying adsorption rate of pure gas, Chem. Eng. Sci. 50 (1995) 549), where pure adsorbate is introduced into a semi-batch adsorber at a constant molar flow rate. The surface diffusivity was determined from the analysis of pressure response versus time, using a linear mathematical model developed earlier. To apply the linear theory over the non-linear range of the adsorption isotherm, we implement a differential increment method on the system which is initially equilibrated with some pre-determined loading. By conducting the experiments at different initial loadings, the surface diffusivity can be extracted as a function of loading. Propane, n-butane, n-hexane, benzene, and ethanol were used as diffusing adsorbate on a commercial activated carbon. It is found that the surface diffusivity of these strongly adsorbing vapours increases rapidly with loading, and the surface diffusion flux contributes significantly to the total flux and cannot be ignored. The surface diffusivity increases with temperature according to the Arrhenius law, and for the paraffins tested it decreases with the molecular weight of the adsorbate. (C) 2002 Elsevier Science Ltd. All rights reserved.

Analysis of adsorption data of graphitized thermal carbon black with a DFT-lattice gas theory

In this paper we analyzed the adsorption of gases and vapors on graphitised thermal carbon black by using a modified DFT-lattice theory, in which we assume that the behavior of the first layer in the adsorption film is different from those of second and higher layers. The effects of various parameters on the topology of the adsorption isotherm were first investigated, and the model was then applied in the analysis of adsorption data of numerous substances on carbon black. We have found that the first layer in the adsorption film behaves differently from the second and higher layers in such a way that the adsorbate-adsorbate interaction energy in the first layer is less than that of second and higher layers, and the same is observed for the partition function. Furthermore, the adsorbate-adsorbate and adsorbate-adsorbent interaction energies obtained from the fitting are consistently lower than the corresponding values obtained from the viscosity data and calculated from the Lorentz-Berthelot rule, respectively.