Reactivity of chars and carbons: New insights through molecular modeling

A new model proposed for the gasification of chars and carbons incorporates features of the turbostratic nanoscale structure that exists in such materials. The model also considers the effect of initial surface chemistry and different reactivities perpendicular to the edges and to the faces of the underlying crystallite planes comprising the turbostratic structure. It may be more realistic than earlier models based on pore or grain structure idealizations when the carbon contains large amounts of crystallite matter. Shrinkage of the carbon particles in the chemically controlled regime is also possible due to the random complete gasification of crystallitic planes. This mechanism can explain observations in the literature of particle size reduction. Based on the model predictions, both initial surface chemistry and the number of stacked planes in the crystallites strongly influence the reactivity and particle shrinkage. Its test results agree well with literature data on the air-oxidation of Spherocarb and show that it accurately predicts the variation of particle size with conversion. Model parameters are determined entirely from rate measurements.

Characterization of pore wall heterogeneity in nanoporous carbons using adsorption: the slit pore model revisited

In this paper, we propose a new nonlocal density functional theory characterization procedure, the finite wall thickness model, for nanoporous carbons, whereby heterogeneity of pore size and pore walls in the carbon is probed simultaneously. We determine the pore size distributions and pore wall thickness distributions of several commercial activated carbons and coal chars, with good correspondence with X-ray diffraction. It is shown that the conventional infinite wall thickness approach overestimates the pore size slightly. Pore-pore correlation has been shown to have a negligible effect on prediction of pore size and pore wall thickness distributions for small molecules such as argon used in characterization. By utilizing the structural parameters (pore size and pore wall thickness distribution) in the generalized adsorption isotherm (GAI) we are able to predict adsorption uptake of supercritical gases in BPL and Norit RI Extra carbons, in excellent agreement with experimental adsorption uptake data up to 60 MPa. The method offers a useful technique for probing features of the solid skeleton, hitherto studied by crystallographic methods.

Superior electric double layer capacitors using ordered mesoporous carbons

This paper reports for the first time superior electric double layer capacitive properties of ordered mesoporous carbon (OMCs) with varying ordered pore symmetries and mesopore structure. Compared to commercially used activated carbon electrode, Maxsorb, these OMC carbons have superior capacitive behavior, power output and high-frequency performance in EDLCs due to the unique structure of their mesopore network, which is more favorable for fast ionic transport than the pore networks in disordered microporous carbons. As evidenced by N-2 sorption, cyclic voltammetry and frequency response measurements, OMC carbons with large mesopores, and especially with 2-D pore symmetry, show superior capacitive behaviors (exhibiting a high capacitance of over 180 F/g even at very high sweep rate of 50 mV/s, as compared to much reduced capacitance of 73 F/g for Maxsorb at the same sweep rate). OMC carbons can provide much higher power density while still maintaining good energy density. OMC carbons demonstrate excellent high-frequency performances due to its higher surface area in pores larger than 3 nm. Such ordered mesoporous carbons (OMCs) offer a great potential in EDLC capacitors, particularly for applications where high power output and good high-frequency capacitive performances are required. (C) 2005 Elsevier Ltd. All rights reserved.

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.

Adsorption of aromatic compounds onto activated carbons: Effects of the orientation of the adsorbates

Adsorption of model aromatic compounds onto two untreated activated carbons with similar physical and chemical properties is investigated. The solution pH of all experiments was lowered so that all solutes were in their molecular forms. It is shown that the difference in the maximum adsorption capacities of the solutes was mainly attributed to the difference in the sizes of the molecules. This new experimental finding is significant to gaining insight into the orientation of the adsorbed phase and hence the adsorption mechanism of aromatic compounds in aqueous solutions. It is shown that the adsorption of aromatic compounds in a stacked motif for pi-pi interactions is unlikely, and in the absence of physical restrictions such as pore width, a T-shaped motif is the preferred orientation.

Density functional theory analysis of the influence of pore wall heterogeneity on adsorption in carbons

Density functional theory for adsorption in carbons is adapted here to incorporate a random distribution of pore wall thickness in the solid, and it is shown that the mean pore wall thickness is intimately related to the pore size distribution characteristics. For typical carbons the pore walls are estimated to comprise only about two graphene layers, and application of the modified density functional theory approach shows that the commonly used assumption of infinitely thick walls can severely affect the results for adsorption in small pores under both supercritical and subcritical conditions. Under supercritical conditions the Henry's law coefficient is overpredicted by as much as a factor of 2, while under subcritical conditions pore wall heterogeneity appears to modify transitions in small pores into a sequence of smaller ones corresponding to pores with different wall thicknesses. The results suggest the need to improve current pore size distrubution analysis methods to allow for pore wall heterogeneity. The density functional theory is further extended here to allow for interpore adsorbate interactions, and it appears that these interaction are negligible for small molecules such as nitrogen but significant for more strongly interacting heavier molecules such as butane, for which the traditional independent pore model may not be adequate.

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.

Adsorption of supercritical fluids in non-porous and porous carbons: analysis of adsorbed phase volume and density

In this paper, we revisit the surface mass excess in adsorption studies and investigate the role of the volume of the adsorbed phase and its density in the analysis of supercritical gas adsorption in non-porous as well as microporous solids. For many supercritical fluids tested (krypton, argon, nitrogen, methane) on many different carbonaceous solids, it is found that the volume of the adsorbed phase is confined mostly to a geometrical volume having a thickness of up to a few molecular diameters. At high pressure the adsorbed phase density is also found to be very close to but never equal or greater than the liquid phase density. (C) 2003 Elsevier Science Ltd. All rights reserved.

Influence of different activated carbons on Ochratoxin A decrease in wines

The presence of mycotoxins in foodstuff is a matter of concern for food safety. Wines can also be contaminated with these toxicants. Several authors have demonstrated the presence of mycotoxins in wine, especially ochratoxin A (OTA) [1]. As these toxicants can never be completely removed from the food chain, many countries have defined levels in food in order to attend health concerns. The maximum acceptable level of OTA in wines is 2.0 µg/kg according to the Commission regulation No. 1881/2006 [2]. Although, higher levels of OTA have been detected in several wine samples. In order to reduce OTA to safer levels, several oenological products can be used in wine; including activated carbons, as shown in previous experiments. Regarding this, the aim of present study was to evaluate the effectiveness of several activated carbons for reducing the amount of OTA present in white and red wines as well as to evaluate their effect on wines physicochemical characteristics. Wine samples were artificially supplemented with OTA at a final concentration of 10.0 µg/L. The different activated carbons were applied at the concentration recommended by the manufacturer in order to evaluate their efficiency in reducing OTA levels. A mixture composed by gelatine, bentonite and activated carbon reduced 80% of OTA concentration in white wine. The same mixture was however less efficient in red wine, achieving only a reduction of 55%. Thereafter, the effect of activated carbon was evaluated in a red wine, achieving reductions of 66%. Considering these results more assays are being performed with other commercial activated carbons, in order to evaluate their efficiency. These results may provide valuable information for winemakers. Knowing the effect of commercial activated carbons they may choose most appropriate products to remove OTA, thus enhancing wine safety and quality.

Incendis històrics a l'alta muntanya pirinenca : anàlisi dels carbons sedimentaris a la torbera de Montarenyo (Lladorre, Pallars Sobirà)

Les zones europees d’alta muntanya, concretament les mediterrànies, han estat utilitzades des de temps remots per l’ésser humà, a través de l’aprofitament de boscos i prats mitjançant activitats com l’agricultura, la ramaderia, la silvicultura i la metal·lúrgia. Però, des de fa temps, amb l’abandonament de les àrees rurals, estem davant d’una falta de gestió dels boscos, degut a la pèrdua de les activitats tradicionals. L’objectiu d’aquest treball és el de determinar l’impacte provocat per les societats antigues sobre els boscos, amb la utilització del foc com a eina de gestió, així com l’anàlisi dels processos d’antropització de les zones de muntanya que utilitzaven aquest recurs. En aquest treball l’anàlisi de l’evolució del paisatge es fa mitjançant l’estudi de les comunitats vegetals històriques i la dinàmica d’incendis, a través de dues metodologies basades en testimonis sedimentaris: l’anàlisi de carbons i l’anàlisi del pol·len. El testimoni sedimentari ha estat extret de la torbera ombrotròfica de Montarenyo, situada a la vessant sud dels Pirineus, a la Vall de Cardós, al Pallars Sobirà. Aquestes dues disciplines han permès indagar en la geohistòria ambiental, per tal d’establir les relacions entre l’ambient i la societat. Els resultats mostren que el foc ha estat utilitzat per nombroses activitats, creant unes dinàmiques forestals característiques. El paisatge actual és conseqüència de les pressions que va haver de patir el bosc durant anys, unes pressions que, amb major o menor mesura han gestionat les masses forestals. Cal doncs conèixer quina ha estat la gestió històrica del bosc per entendre’n el seu estat actual i poder escollir la gestió més adequada per conservar-lo.

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

Data of methylene blue number and iodine number of activated carbons samples were calibrated against the respective surface area, micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.

Els Carbons activats del LEQUIA: noves perspectives en l'aprofitament dels fangs de depuradora

Els fangs que produeixen les depuradores estan esdevenint, pel seu volum, un problema que demana solucions. La via del compostatge no exhaureix la producció i en condiciona l'ús com a combustible o com a matèria primera per a l'obtenció de carbons activats. Els carbons activats tenen grans aplicacions en la indústria moderna. El LEQUIA de la UdG ha desenvolupat una nova metodologia per a l'obtenció d'aquest producte a partir dels fangs, que permet uns rendiments que els ha de fer atractius per a la seva industrialització. En el procés, a més, s'obté hidrogen i biodièsel en quantitats interessants

Pyrolysis of polymer-derived carbons in the formation of graphitizing carbons and nanoparticles of zirconia

Carbons have been prepared by the low-temperature pyrolysis, under argon, of a number of long-chain polymers. We have found that the resistivity (Omega cm(-1)) varies considerably with the temperature of pyrolysis; thus, for ammonium polyacrylate, the resistivity of that pyrolyzed at 600 degrees C is 9.7 x 10(4) Omega cm(-1) whereas that pyrolyzed at 1000 degrees C is ca. 3 Omega cm(-1). A similar situation arises for the other polymers studied (including radiolyzed cross-linked polyacrylamide). All those pyrolyzed at 600 degrees C had a resistivity of > 1 x 10(6) Omega cm(-1), whereas those pyrolyzed at 1000 degrees C had a resistivity of ca. 3-5 Omega cm(-1). A notable exception was that of unirradiated polyacrylamide, where the resistivity remained at > 1 x 10(6) Omega cm(-1) over the range of temperatures studied. The decrease of resistivity with increase of temperature of pyrolysis has been related to the formation of glassy carbon. Nanoparticles (4 nm) of tetragonal zirconia were formed when zirconium polyacrylate was pyrolyzed under similar conditions.