An evaluation of the reliability of the characterization of the porous structure of activated carbons based on incomplete nitrogen adsorption isotherms

The paper presents the results of research devoted to reliability evaluation of the analysis of results of the porous structure of activated carbons based on incomplete nitrogen adsorption isotherms using the BET, t-plot, and NLDFT methods, as well as the LBET method comprising the unique numerical fast multivariant procedure of adsorption system identification. The research involved the application of the nitrogen adsorption isotherms obtained for five samples of activated carbons produced from waste materials of organic origin by way of chemical activation with potassium hydroxide, sodium hydroxide, and potassium carbonate with the use of microwave heating. The analyses performed pointed to a good correlation between the results obtained using the BET, t-plot, NLDFT, and LBET methods. Moreover, the parameters of the porous structure determined using these methods based on incomplete adsorption isotherms of nitrogen are in fact as reliable as these methods allow.     

Production of granular activated carbons from select agricultural by-products and evaluation of their physical,chemical and adsorption properties

Representative samples of soft, low density, group 1 (rice straw, rice hulls, sugarcane bagasse) and hard, high density, group 2 agricultural by-products (pecan shells) were converted into granular activated carbons (GACs). GACs were produced from group 1 and 2 materials by physical activation or from group 2 materials by chemical activation. Carbons were evaluated for their physical (hardness, bulk density), chemical (ash, conductivity, pH), surface (total surface area), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. The results show that the type of by-product, binder, and activation method determine the properties of GACs. Regardless of the binder, sugarcane bagasse showed a better potential than rice straw or rice hulls as precursor of GACs with the desirable properties of a sugar decolorizing carbon. Pecan shells produced GACs that were closest to the reference carbons in terms of all the properties investigated.     

Convenient experimental determination of adsorption isotherms in a Hydrophobic Interaction Chromatography system

Summary HPLC was combined with a packable microbore guard column to obtain the adsorption isotherm of lysozyme in a Hydrophobic Interaction Chromatography system. The equipment configuration enabled isotherm determination of the protein on a relatively low pressure chromatographic media (TosoHaas 650M Phenyl).Notation C_m,i is the mobile phase concentration of protein. (M/L³ _(liquid)) - C_m,0 =0 - C_s,i is the stationary phase concentration of protein. It is the concentration of protein on the chromatographic media. (M/L³ _(solid)) - C_s,0 =0 - M,L is the dimensions mass and length - V_r,i is the retention volume of the peak front that corresponds to a mobile phase protein on the concentration C_m,i. (L³ _(liquid)) - i i is a counter that is used to keep track of C_m, C_s, and V_r.For example, i=1 in the term C_m,i denotes the first, and lowest, mobile phase protein concentrations are described by higher values of i. - V_d is the system dead volume. It consists of all of the system volume that the mobile phase "sees" or contacts, includingchromatographic media interparticle and pore volume. (L³ _liquid) - V_s the stationary phase volume. V_s is the nonporous bead volume. For porous beads, V_s is the bead volume - the porevolume. (L³ _(solid)) - V_e is the empty column volume. (L³ _liquid) - V_m is the packed column mobile phase volume and consists of the pore volume and the excluded volume. (L³ _(liquid)) - V_{e system} is the empty column system volume. (L³ _(liquid)) - V_frit the volume of mobile phase that fills the column frits. (L³ _(liquid)) - V_woc the system volume without the column connected. (L³ _(liquid))     

pH effects on the adsorption of saxitoxin by powdered activated carbon

Increasing occurrence of cyanotoxins in surface waters worldwide pose significant problems, including those for drinking water utilities. In this study, the removal of saxitoxin (STX) from three different powdered activated carbons (PACs) was studied. STX is one of the most toxic paralytic shellfish toxins (PSTs), albeit not the most prevalent. The results showed that a wide range of non-electrostatic and electrostatic interactions appeared to play a role in the sorption of STX on PAC, depending on the solution pH, NOM concentration, and other factors. A bituminous coal-based PAC, that was studied in greatest detail, showed a trend of increasing sorption capacity for STX with increasing pH. NOM appeared to significantly inhibit adsorption when the pH was nearly neutral (e.g. 7.05), yet it had less effect at higher pH levels of 8.2 and 10.7.     

Dye adsorption by sewage sludge-based activated carbons in batch and fixed-bed systems

The present research work deals with the production of activated carbons by chemical activation and pyrolysis of sewage sludges. The adsorbent properties of these sewage sludges based activated carbons were studied by liquid-phase adsorption tests. Dyes removal from colored wastewater being a possible application for sludge based adsorbents, methylene blue and saphranine removing from solution was studied. Pure and binary adsorption assays were performed in batch and fixed bed systems. In all cases studied, the adsorbents produced from sewage sludges were able to adsorb both the compounds considered here. Nevertheless, time required for reaching equilibrium, adsorptive capacity and fixed bed characteristic parameters were different for these two compounds. Methylene blue adsorption occurred faster than that of saphranine, and it was preferably adsorbed when treating binary solutions. It could be concluded that the sewage sludge-based activated carbons may be promising for dyes removal from aqueous streams.     

Water adsorption isotherms of lipids

Hydration of bilayer lipids is a fundamental property of biological membranes. The available database of lipid hydration isotherms is fitted over the entire range of water activities by using a statistical mechanical approach that is an extension of the common Brunauer-Emmett-Teller model, to include differential energies of association for water molecules beyond the first strongly bound layer. Three-parameter fits are obtained that can be used to represent the experimental isotherms to a good degree of accuracy over the complete range of water-binding activities. Fits are also made in terms of the hydration pressure and correlation length of water ordering, by using the polarization theory of lipid hydration. The relationship of the latter approach to measurements of hydration forces between lipid bilayers is discussed.     

Application of adsorption isotherms to chromium adsorption onZ.ramigera

Summary Adsorption isotherms for the adsorption of chromium onZoogloea ramigera are developed. The rates were affected by the pH and temperature of adsorption medium. The biomass ofZ. ramigera at pH 2.0 where the optimum pH for biosorption lies exhibited the highest chromium adsorptive uptake capacity. In general, higher adsorptive uptake was observed at 25°C than 35°C and 45°C.     

Surface properties of granular activated carbons from agricultural by-products and their effects on raw sugar decolorization

Granular activated carbons (GACs) were produced from sugarcane bagasse combined with one of two binders (corn syrup, coal tar) by physical activation and from pecan shells by physical and chemical activation. GACs were evaluated for their physical (hardness, bulk density), chemical (ash, pH), surface (surface area, pore size distribution, surface chemistry), and adsorption properties (molasses color removal, sugar decolorization) and compared with two commercial reference carbons. Results showed that larger surface area, a well-developed macro- and mesoporosity, and a minimal surface charge were desirable in GACs designed for sugar decolorization. Steam activation of pecan shells carbon was the only by-product-activation combination that produced GAC with all the above three desirable characteristics of a good sugar decolorizer. Chemical activation of pecan shells yielded GACs with high surface area and adequate pore size distribution but with large surface charge. In contrast, sugarcane bagasse-based GACs exhibited low surface areas and unsatisfactory physical/chemical properties.     

Physical and chemical properties of selected agricultural byproduct-based activated carbons and their ability to adsorb geosmin

The objectives of this study were to evaluate selected physical and chemical properties of agricultural byproduct-based activated carbons made from pecan shells and sugarcane bagasse, and compare those properties to a commercial coal-based activated carbon as well as to compare the adsorption efficiency of these carbons for geosmin. Comparison of the physical and chemical properties of pecan shell- and bagasse-based carbons to the commercial carbon, Calgon Filtrasorb 400, showed that pecan shell carbon, but not the bagasse carbon, compared favorably to Filtrasorb 400, especially in terms of surface area, bulk density, ash and attrition. A carbon dosage study done in a model system showed the amount of geosmin adsorbed to be greater for Filtrasorb 400 and the bagasse-based carbon at low carbon concentrations than for the pecan shell carbons, but geosmin adsorption was similar in all carbons at higher carbon dosages. Application of the Freundlich isotherm model to the adsorption data showed that carbons made by steam activation of pecan shells or sugarcane bagasse had geosmin adsorption characteristics most like those of the commercial carbon. In terms of physical, chemical and adsorptive properties, steam-activated pecan shell carbon most resembled the commercial carbon and has the potential to replace Filtrasorb 400 in applications involving removal of geosmin from aqueous environments.     

Effect of the concentration of inherent mineral elements on the adsorption capacity of coconut shell-based activated carbons

Coconut shells of West Africa Tall, a local variety of the coconut species Cocos nucifera L., were taken from five different geographical locations in Ghana and examined for the presence and concentration levels of some selected mineral elements using atomic absorption spectrometer. Activated carbons were subsequently made from the shells by the physical method. The iodine adsorption characteristics of the activated carbons measured showed a definite relationship to the concentration levels of potassium and other mineral elements in the precursor shell. Samples with lower total minerals content recorded higher iodine numbers. It was observed that the origin of the shells was related to the concentration levels of the analyzed mineral elements in the shells, which in turn affected the adsorption capacity of the activated carbons. The results of this study have important implications for the sourcing of coconuts whose shells are used in the manufacture of activated carbons.     

Enhanced biodegradation ofo-cresol by activated sludge in the presence of powdered activated carbon

Summary Addition of powdered activated carbon to a continuous-flow activated-sludge culture in a gas-lift bioreactor growing on o-cresol in a mineral-salts medium resulted in a reduction of the effluent o-cresol concentration during steady-state conditions as well as during shock-load conditions. During the latter conditions the activated carbon acted as a buffer. Bioregeneration of loaded activated carbon did occur, resulting in enhanced biodegradation of o-cresol. Adsorption of o-cresol by activated carbon was not sufficient to explain the total difference in effluent o-cresol concentration between the system with activated carbon and the system without activated carbon. Offprint requests to: R. J. de Jonge     

Enhanced adsorption of phenolic compounds, commonly encountered in olive mill wastewaters, on olive husk derived activated carbons

Olive husk was used for the preparation of activated carbon by chemical activation with KOH. The effects of carbonization and activation time on carbon properties were evaluated. The surface area of the produced carbons was measured by means of N(2) adsorption at 77K. The carbons with the highest surface area were further characterized by means of elemental analysis, particle size measurement, Boehm titration, zeta potential measurement, and temperature programmed desorption (TPD). Subsequently they were used for adsorption of a mixture of polyphenols consisting of caffeic acid, vanillin, vanillic acid, pi-hydroxybenzoic acid and gallic acid at two temperatures, and their adsorptive capacity was compared to a commercial carbon Acticarbon CX and found to be higher enough. The role of the porosity and surface groups are discussed in relation to the adsorption forces and the properties of the adsorbed substances. A thermodynamic interpretation of the results is also attempted.     

Purification of sugar beet vinasse - adsorption of polyphenolic and dark colored compounds on different commercial activated carbons

The adsorption on activated carbons of dark colored compounds contained in sugar beet vinasse was studied. Four commercial activated carbons with different properties (particle size, residual acidity and microporous properties) were respectively checked for efficiency at two temperature levels (25 °C and 40 °C) and at four pH levels (2, 3.5, 7, 10). The adsorption of organic molecules was determined by quantifying the amounts of total polyphenolic compounds and total organic carbon. The results showed that the adsorption capacity of dark colored compounds was enhanced by the decrease in both temperature and pH values of the solution. In this study, it is shown that this capacity depends on activated carbon characteristics which can be classified in the following order: particle size > residual acidity > microporous volume. Three models (Langmuir, Freundlich and Dubinin–Radushkevich) were tested from experimental data and compared. The Langmuir model provided the best correlation on all the activated carbons studied.     

Ammonia adsorption in a fixed bed of activated carbon

The rise in atmospheric pollution caused by gases such as ammonia has led many researchers to conduct studies aimed at decreasing or treating the emissions of such polluting gases. The present work attempted to study the adsorption of ammonia in the fixed bed of activated carbon as a means to treat its emissions. The effects of the initial concentration of ammonia (C0) and of the bed temperature (TL) on the adsorption of ammonia by the activated carbon were also considered. Adsorption capacity of activated carbon was determined using data from the breakthrough curves and from a balance of mass in the bed. Adsorption capacities were obtained employing the Langmuir and Freudlich isotherms. The results showed that within the NH3 concentration range of 600-2400 ppm, adsorption capacity varied from 0.6 to 1.8 mg NH3/g carbon at 40 degrees C, from 0.2 to 0.7 mg NH3/g carbon at 80 degrees C and from 0.15 to 0.35 mg NH3/g carbon at 120 degrees C. These numbers highlight the tendency toward a lower adsorption capacity with the decrease in temperature. As to mass of the bed, this latter variable had no significant influence over adsorption capacity.     

Biodegradation of BTEX by bacteria on powdered activated carbon

Aerobic degradation of a mixture of benzene, toluene, ethylbenzene and the mixed xylenes (BTEX) by a mixed bacterial population was studied in a continuously fed, completely mixed bioreactor in the presence of powdered activated carbon (PAC). Adsorption was characterized in the presence and in the absence of bacteria on PAC, and the affinity of virgin PAC to individual BTEX components was shown to be inversely correlated to their solubility in water. Bacteria colonizing the PAC particles are essential for simultaneous adsorption–biodegradation processes. In order to restrict biofilm formation and thereby mass transfer resistance of pollutants from the bulk to the PAC, the slurry was recirculated in the reactor system using a high shear pump. The bacteria on the PAC surface were constantly in a flux between the adsorbed and free phase, a phenomenon that prevented the formation of a biofilm on the PAC surface and thereby extended the life of the PAC.     

A novel method of analysis of ligand-polynucleotide adsorption isotherms]

The adsorption of ethidium bromide on the synthetic double-stranded polyribonucleotide poly(G)poly(C) was investigated by adsorption spectroscopy. The adsorption isotherms were analyzed in the framework of the Crothers-Gursky model. It was shown that adsorption parameters (e.g., binding constant) may also be determined from the analysis of dispersion of some bound molecules. In some cases this method may be more convenient.     

Reliable prediction of adsorption isotherms via genetic algorithm molecular simulation

Conventional molecular simulation techniques such as grand canonical Monte Carlo (GCMC) strictly rely on purely random search inside the simulation box for predicting the adsorption isotherms. This blind search is usually extremely time demanding for providing a faithful approximation of the real isotherm and in some cases may lead to non-optimal solutions. A novel approach is presented in this article which does not use any of the classical steps of the standard GCMC method, such as displacement, insertation, and removal. The new approach is based on the well-known genetic algorithm to find the optimal configuration for adsorption of any adsorbate on a structured adsorbent under prevailing pressure and temperature. The proposed approach considers the molecular simulation problem as a global optimization challenge. A detailed flow chart of our so-called genetic algorithm molecular simulation (GAMS) method is presented, which is entirely different from traditions molecular simulation approaches. Three real case studies (for adsorption of CO₂ and H₂ over various zeolites) are borrowed from literature to clearly illustrate the superior performances of the proposed method over the standard GCMC technique. For the present method, the average absolute values of percentage errors are around 11% (RHO-H₂), 5% (CHA-CO₂), and 16% (BEA-CO₂), while they were about 70%, 15%, and 40% for the standard GCMC technique, respectively.     

Cometabolic bioregeneration of activated carbons loaded with 2-chlorophenol

Thermally and chemically activated carbons were used to investigate the extent of cometabolic bioregeneration in laboratory scale activated sludge reactors. Bioregeneration was determined and quantified by measuring the substrate and chloride concentrations, oxygen uptake rates, and deterioration in adsorption capacities. Activated carbons loaded with 2-chlorophenol could be partially bioregenerated in the presence of phenol as the growth substrate. The occurrence of exoenzymatic bioregeneration was also possible during cometabolic bioregeneration of thermally activated carbons. However, cometabolic bioregeneration of chemically activated carbons was much superior compared with thermally activated carbons. In cometabolic bioregeneration of activated carbons loaded with 2-chlorophenol, biodegradation, rather than desorption, was the rate-limiting step. Environmental Scanning Electron Microscopy analyses showed that groups of cocci-shaped phenol-oxidizers were attached to the outer surface or internal cavities of activated carbon as a fingerprint of bioregeneration.     

Immobilization of Acetobacter acoti on cellulose ion exchangers: adsorption isotherms

The adsorptive behavior of cells of Acetobacter aceti, ATCC 23746, on DEAE-, ECTEOLA-, TEAE-, and DEHPAE-cellulose ion exchangers in a modified Hoyer's medium at 30 degrees C was investigated. The maximum observed adsorption capacities varied from 46 to 64 mg dry wt/g resin. The Langmuir isotherm form was used to fit the data, since the cells formed a monolayer on the resin and exhibited saturation. The equilibrium constant in the Langmuir expression was qualitatively correlated with the surface charge density of the resin. The adsorption was also "normalized" by considering the ionic capacities of the resins. The exceptionally high normalized adsorption capacity of ECTEOLA-cellulose, 261 mg dry wt/meq, may be explained by an interaction between the cell wall and the polyglyceryl chains of the exchanging groups in addition to the electrostatic effects. The effect of pH on the bacterial adsorption capacity of ECTEOLA-, TEAE-, and phosphate-cellulose resins was studied and the pl of the bacteria was estimated to be 3.0.