I.P.P. Cansado

Reference data for the adsorption of methanol on carbon materials

The adsorption of methanol at 298 K on carbon blacks and microporous carbons, including Carbosieve, Takeda molecular sieves, Maxsorb superactivated carbons and an activated charcoal cloth, has been studied. Analysis of the results indicates that the mechanism of adsorption of methanol on carbon blacks shows some similarities to that of water vapour. However, it is still possible to define reference data which can be used to obtain estimates of the surface area of carbon blacks, provided that the surface is reasonably polar, and of external surface area and micropore volume of microporous carbon adsorbents, provided that the pore size is not very large.

Reference data for the adsorption of dichloromethane on carbon materials

Abstract The adsorption of dichloromethane at 298K on non-porous carbon blacks and microporous activated carbons, including Takeda molecular sieves and Maxsorb superactivated carbons, has been studied. The results suggest that the exact shape of the isotherm on non-porous carbons is sensitive to the degree of uniformity of the surface and that it is therefore not possible to define a universal standard dichloromethane isotherm. On the other hand, it is possible to define reference data which can be used to analyse adsorption isotherms of dichloromethane determined on non-porous and microporous carbon materials by means of the α s method. An indication of the range of applicability and the likely precision obtained when using the data is given.

Adsorption Properties of Activated Carbons Prepared from Recycled PET in the Removal of Organic Pollutants from Aqueous Solutions

Activated carbons (ACs) were prepared from recycled polyethylene terephthalate (PET) by chemical activation with KOH and used successfully for the removal of 4-chloro-2-methylphenoxyacetic acid (MCPA) and Methylene Blue (MB) from aqueous media. In order to improve the adsorption capacity towards pollutant removal, the AC was submitted to different post-treatments. After oxidation, the sample exhibited an increase in MB adsorption capacity but showed a decreased MCPA adsorption removal extent. High-temperature treatment was not favourable for increasing the MB or MCPA adsorption capacity. However, after treatment with sodium hydroxide or urea, the samples showed a significant increase in their MCPA adsorption capacities. Normalisation of the MB and MCPA adsorption data with respect to the micropore volume led to a clearer understanding of the influence of the textural and chemical characteristics of the AC on the removal of MB and MCPA. The MB and MCPA adsorption isotherms were analysed via the Langmuir and Freundlich models, with the calculated parameters accurately fitting the experimental data and exhibiting good agreement between them.

Designing activated carbons from natural and synthetic raw materials for pollutants adsorption

Over the last decades the literature has shown the possibility of producing activated carbons (AC) from a wide variety of raw materials, and to use them as one of the most environment-friendly solutions for waste disposal [1]. Simultaneously, it has been shown that the adsorption of pollutants from different sources by activated carbons is one of the most efficient techniques for remediating or solving this kind of problem [2]. In this context, phenolic compounds represent one of the most important classes of pollutant present in the environment [3]. In this perspective, we present a study involving the production of AC from cork (Quercus suber L.), PEEK (polyetheretherketone) wastes or granulated recycled PET (polyethyleneterephthalate) and their applicability for the adsorption of phenolic compounds from the liquid phase. All samples were characterised in relation to their structural properties and chemical composition, by different techniques, including nitrogen adsorption at 77 K, elemental analysis (C, H, N, O and S) and point of zero charge (PZC). The activated carbons produced demonstrated high adsorption capacities both in the gas and liquid phase as exemplified by N2 and phenolic compounds adsorption experiments. Based on the structural and chemical properties, and on the kinetic and equilibrium studies of liquid phase adsorption, it is possible to conclude that it is the porous volume of the ACs that predominantly controls the process of phenolic compounds adsorption.

Synthetic polymers blend used in the production of high activated carbon for pesticides removals from liquid phase.

ABSTRACT For the activated carbon (AC) production, we used the most common industrial and consumer solid waste, namely polyethyleneterephthalate (PET), alone or blended with other synthetic polymer such polyacrylonitrile (PAN). By mixing PET, with PAN, an improvement in the yield of the AC production was found and the basic character and some textural and chemical properties were enhanced. The PET–PAN mixture was subjected to carbonisation, with a pyrolysis yield of 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The AC revealed a high surface area (1400, 1230 and 1117 m2 g−1) and pore volume (0.46, 0.56 and 0.50 cm3 g−1), respectively, for PET, PAN and PET–PAN precursors. Selected ACs were successfully tested for 4-chloro-2-methylphenoxyacetic acid (MCPA) and diuron removal from the liquid phase, showing a higher adsorption capacity (1.7 and 1.2 mmol g−1, respectively, for MCPA and diuron) and good fits with the Langmuir (PET) and Freundlich equation (PAN and PET–PAN blend). With MCPA, the controlling factor to the adsorption capacity was the porous volume and the average pore size. Concerning diuron, the adsorption was controlled essentially by the external diffusion. A remarkable result is the use of different synthetic polymers wastes, as precursors for the production of carbon materials, with high potential application on the pesticides removals from the liquid phase.

Textural Development of Activated Carbon Prepared from Recycled PET with Different Chemical Activation Agents

Activated carbons (AC) were prepared from waste granulated Polyethyleneterephthalate (PET) by chemical activation with phosphoric acid, sodium hydroxide and potassium hydroxide. All AC were characterised by N2 adsorption at 77 K, and those prepared with H3PO4 had a narrow pore size around 0.8 nm, those prepared with NaOH had a larger pore size higher than 1.52 nm and those prepared with KOH presented a pore size varying between 0.66 and 1.58 nm. The results suggest that H3PO4 and NaOH are not the most suitable activating agents for preparing AC with a high pore volume from waste PET. The AC produced with KOH presented a very high porosity, which passed through a maximum of 0.75 cm3g-1, due to an enlargement of the small micropores with an increase of the carbonisation temperature.

On the Lo/σ Range of the TVFM

Adsorption isotherms of nitrogen, carbon dioxide, methanol, dichloromethane, benzene and neopentane were determined on a range of molecular sieve and super-activated carbons with the objective of establishing the range of validity of the Theory of Volume Filling of Micropores (TVFM) in terms of the ratio of pore width to molecular diameter, Lo/σ. It is shown that, in the absence of molecular-sieving effects, both the characteristic curve concept and the DR equation are valid over the whole of the micropore range, corresponding to values of Lo/σ less than or equal to 5 and to at least a slight enhancement in the characteristic energy, E0, of the adsorbent when compared with the corresponding value obtained with non-porous carbon blacks. On the other hand, estimation of the mean micropore width was only possible for values of Lo/σ up to ca. 2.3, corresponding to at least a two-fold enhancement in E0. Results obtained using N2 at 77 K showed some significant differences to those obtained with organic adsorptives at higher temperature.

Activated Carbons Prepared from Natural and Synthetic Raw Materials with Potential Applications in Gas Separations

A carbon molecular sieve for the purification of a gas mixtures containing O2, N2 and CO2, CH4 was produced from a waste granulated PET by means of a single carbonisation step at 973 K. Activated carbon materials presenting good adsorption capacity and some selectivity for O2/N2 and CO2/CH4 were prepared from granulated PET and cork oak with pore mouth narrowing using CVD from benzene. The diffusion coefficients of O2, N2, CO2 and CH4 in these materials were calculated and are comparable to published values determined on Takeda 3A and on a carbon molecular sieve prepared from PET textile fibres by means of carbonisation and subsequent CVD with benzene. However, the selectivities were not quite as good as those given by Takeda 3A. However, taking into account that this is a first attempt at producing CMS from PET, the results are encouraging, and it is to be expected that further development of the experimental procedure will result in new materials with improved performance.

Hydrothermal Stability of Ordered Mesoporous Titanosilicate Materials Prepared at Room Temperature

A study of hydrothermal stability, performed in boiling water under static conditions, of MCM-41 materials containing different titanium content, prepared by direct synthesis at ambient temperature and pressure, using tetraethoxysilane, titanium ethoxide and octadecyltrimethyl- ammonium bromide is presented. The behaviour is compared with pure silica grades prepared by a similar procedure. The samples were characterised by X-ray diffraction, adsorption of nitrogen at 77K and diffuse reflectance UV–Vis spectroscopy. It was found that the stability improves as the amount of titanium increases and that Ti-MCM-41 samples prepared with Si/Ti≤50 are significantly stable. After 12h in boiling water the pore size uniformity was practically maintained and only a small decrease in pore volume (5-9%), total surface area (2-7%) and mesopore width (3%) and a slight increase in pore wall thickness (3-6%) occurred. In contrast, some degradation of the MCM-41 structure for the pure silica and the lower Ti content (Si/Ti=100) samples was observed with the effect being less pronounced for the latter. The higher hydrothermal stability of titanium substituted samples is probably correlated with a higher degree of polymerisation of the pore walls and with the presence of extra framework titanium.

Valorisation of Tectona Grandis tree sawdust through the production of high activated carbon for environment applications

This work presents a first approach concerning the use of Tectona Grandis tree sawdust (from East Timor) for high activated carbon production, by physical activation with carbon dioxide at different temperatures. The activated carbons (AC) obtained exhibit a well-developed porous structure with a pore size distribution varying from micro to mesopores. Selected AC was successfully evaluated for pesticide removal, specific to 4-chloro-2-methylphenoxyacetic acid, from the liquid phase. The results presented are very promising, allowing to establish that Tectona Grandis sawdust is as an excellent precursor for the basic AC production and allow to expect good performance of theses adsorbents on the removal of a broad range of pollutants. It should also be noted that, this achievement is very relevant for developing countries, such East Timor, where Tectona Grandis sawdust is available and may constitute a source of income creating a handle to the technical and industrial development of this region.