Pedro M. Álvarez

Activated carbon modifications to enhance its water treatment applications. An overview.

The main objective of this study was to list and compare the advantages and disadvantages of different methodologies to modify the surface of activated carbons (ACs) for their application as adsorbents to remove organic and inorganic pollutants from aqueous phase. These methodologies have been categorized into four broad groups: oxidation, sulfuration, ammonification, and coordinated ligand anchorage. Numerous investigations into the removal of metals from water have modified carbon surfaces to increase their content of acidic surface functional groups by using H(2)O(2), O(3) and HNO(3). Because these treatments can reduce the AC surface area, researchers are seeking alternative methods to modify and/or create surface functional groups without the undesirable effect of pore blockage. The nitrogenation or sulfuration of the AC surface can increase its basicity favoring the adsorption of organic compounds. The introduction of nitrogen or sulfur complexes on the carbon surface increases the surface polarity and, therefore, the specific interaction with polar pollutants. Different coordinated ligands have also been used to modify ACs, showing that coordinated ligand anchorage on the AC surface modifies its textural and chemical properties, but research to date has largely focused on the use of these modified materials to remove heavy metals from water by complexes formation.

Kinetics of Heterogeneous Catalytic Ozone Decomposition in Water on an Activated Carbon

Abstract Ozone decomposition in water in the presence of an activated carbon has been studied. Variables investigated were agitation speed, carbon particle size, temperature and pH. In all cases, the presence of activated carbon improved the ozone decomposition rate. Between pH 2 and 7 the ozone decomposition rate due to both the homogeneous and heterogeneous mechanisms hardly varied while a significant increase was noticed with increasing pH. A kinetic study based on a Langmuir-Hinselwood type mechanism for the heterogeneous surface reaction was undertaken. According to this mechanism the heterogeneous ozone decomposition kinetics can be simplified to follow a first order process. Fit of experimental results to the kinetic equations derived from the mechanism allowed for the determination of the apparent first order rate constants of the ozone surface heterogeneous reaction and adsorption equilibrium constants.

Diclofenac removal from water with ozone and activated carbon

Diclofenac (DCF) has been treated in water with ozone in the presence of various activated carbons. Activated carbon-free ozonation or single ozonation leads to a complete degradation of DCF in less than 15 min while in the presence of activated carbons higher degradation rates of TOC and DCF are noticeably achieved. Among the activated carbons used, P110 Hydraffin was found the most suitable for the catalytic ozonation of DCF. The influence of pH was also investigated. In the case of the single ozonation the increasing pH slightly increases the TOC removal rate. This effect, however, was not so clear in the presence of activated carbons where the influence of the adsorption process must be considered. Ecotoxicity experiments were performed, pointing out that single ozonation reduces the toxicity of the contaminated water but catalytic ozonation improved those results. As far as kinetics is concerned, DCF is removed with ozone in a fast kinetic regime and activated carbon merely acts as a simple adsorbent. However, for TOC removal the ozonation kinetic regime becomes slow. In the absence of the adsorbent, the apparent rate constant of the mineralization process was determined at different pH values. On the other hand, determination of the rate constant of the catalytic reaction over the activated carbon was not possible due to the effect of mass transfer resistances that controlled the process rate at the conditions investigated.

Enhanced adsorption of metal ions onto functionalized granular activated carbons prepared from cherry stones

Some granular activated carbons (GACs) were prepared from cherry stones (CS), an agricultural waste, by thermal methods following pyrolysis in nitrogen and subsequent activation (with air, carbon dioxide and steam) or single-step activation in steam. A GAC prepared by activation with carbon dioxide was further treated with several oxidizing agents (air, air-ozone mixture, nitric acid and hydrogen peroxide). The non-oxidized GACs produced have surface areas ranged from 508 to 901m(2)/g and show a predominantly micro- and macropores structure. Oxidation treatments, especially with nitric acid and ozone, led to the fixation of high amounts of acidic surface oxygen complexes (SOCs), thus making the carbon surface more hydrophilic. Contrary to oxidation with the other agents, the ozone treatment, at the conditions applied in this work, does not decrease the GAC surface area. Both, the non-oxidized and the oxidized GACs were used as adsorbent to study the adsorption of Cu(II) from aqueous solution. Adsorption isotherms were obtained at 25 degrees C and data were well fitted to the Langmuir equation. The results show that the Cu(II) uptake of the non-oxidized GACs is not great, but similar to that of the commercial grade Filtrasorb 400. The adsorption capacity for Cu(II) could be greatly enhanced by GAC oxidation, especially with nitric acid and ozone treatments. The larger adsorption capacity of the oxidized GACs has been attributed to oxygen functionalities (mainly carboxylic) fixed on the GAC surface, which can remove Cu(II) species from water by both ion-exchange and surface complexation mechanisms. The ozonated GAC was also evaluated for the adsorption of Co(II) species from single solute and Cu(II)-Co(II) binary mixture solutions. The functionalization of GAC by the ozone treatment improved the adsorption of both Cu(II) and Co(II) regardless of the fact that they were in single solute or binary systems.

Activated Carbon Adsorption of Some Phenolic Compounds Present in Agroindustrial Wastewater

Single solute and simultaneous experimental adsorption isotherms of three phenolic compounds: gallic acid, p-hydroxybenzoic acid and syringic acid, have been investigated at 20, 30 and 40°C, using a bituminous coal based activated carbon. Regardless of temperature, the capacity of the activated carbon used to adsorb these compounds presented the following order: syringic acid > p-hydroxybenzoic acid > gallic acid. The increase of temperature slightly favored the adsorption capacity of the phenolic compounds. In binary and ternary component adsorption, experimental data suggest that interactions between adsorbates improve the adsorption capacity of some of the phenolic acid compounds. On the contrary, at high organic concentrations, adsorbed gallic acid was partially removed from the activated carbon surface because of the presence of the other components.

Fenton Reagent Advanced Oxidation of Polynuclear Aromatic Hydrocarbons in Water

Aqueous oxidation of three polynuclear aromatic hydrocarbons, fluorene, phenanthrene and acenaphthene with the combination of hydrogen peroxide and ferrous ion, Fenton reagent, has been studied. The effect of variables such as concentration of both reactants, pH and presence of bicarbonate ion and humic substances has been investigated. Products resulting from oxidation have also been identified. From experimental results and kinetic data determined the process is confirmed as an advanced oxidation involving the generation of hydroxyl radicals. Oxidation rates are even higher than those from other advanced oxidation systems involving ozone, UV radiation and hydrogen peroxide. Reactivity is in the following decreasing order: Phenanthrene > Fluorene > Acenaphthene.

Formation of oxygen complexes by ozonation of carbonaceous materials prepared from cherry stones: I. Thermal effects

Abstract In this study, the feasible use of ozone to form oxygen complexes in chars prepared from cherry stones (CS) is investigated. CS were charred at 450, 600 or 900°C for 2 h in nitrogen. Char samples were ozonated over the 25–250°C temperature range for 1 h. Elemental chemical analysis was effected for a few selected samples. The oxygen complexes were successfully analyzed by Fourier infrared spectroscopy (FT-IR) and by titration methods. Thermal decomposition of ozone in the gas stream was also studied and the mechanism of the ozonation process dealt with. The ozonation treatment of CS chars was found to yield products with a relatively high concentration of a number of oxygen complexes. These include phenolic hydroxyl, quinonic, carboxylic acid, and ether structures. The content of lactonic structures was very low in the ozonated samples. The type and quantity of oxygen complexes depended on the ozonation and charring temperatures. The formation of oxygen complexes was favored when the charring of CS was effected at 450°C and when the ozonation of the char prepared at 600°C was performed at 100°C. The ozone content in the gas stream was very sensitive to the temperature increase in the reactor. Several reaction routes have been proposed for the transformation of ether, aromatic, and olefinic structures present in CS chars into oxygen complexes.

pH sequential ozonation of domestic and wine-distillery wastewaters

Domestic and wine-distillery wastewaters were treated by semi-batch and continuous pH sequential ozonations. The process involves a succession of acidic and alkaline wastewater pH conditions. The alkaline periods allow oxidation of organic matter by hydroxyl radical and produce carbonates that eventually would inhibit the oxidation. On the other hand, the acidic periods favour the development of direct ozone reactions and strip off carbonates as carbon dioxide from the wastewater. Experimental results of pH sequential ozonation showed degradation and removal rates of wastewater pollutants higher than those achieved at constant either acidic or basic pH. The most significant improvement of ozone efficiency and pollutants removal were obtained by controlling the number of cycles, pH and time of acidic and alkaline phases. Also, ozonated wastewaters showed high biodegradability as deduced from their BOD/COD ratios. The feasibility of treating domestic and wine-distillery wastewater by an integrated activated sludge (ASP)-pH sequential ozonation system was evaluated. Integrated ASP-ozonation at constant pH processes were also carried out for comparative purposes. In these combined experiments, pH sequential ozonation showed advantages compared to ozonation at constant pH in reducing global parameters such as COD, TOC and TKN, but ozonation at constant pH led to higher removal of polyphenols and UV254 absorbing compounds.

Optimisation of Fenton’s reagent usage as a pre-treatment for fermentation brines

Pre-treatment of fermentation brines from green olives has been carried out by the Fe(II)/Fe(III)/H(2)O(2) system. Reagent concentration exerted a positive influence on chemical oxygen demand (COD) removal. Hydrogen peroxide uptake showed values in the range 0.3-1.6mol of COD eliminated per mol of H(2)O(2) consumed depending on operating conditions. The optimum working pH was found to be in the interval 2.0-3.5. Reaction temperature increased the COD degradation rate, although similar COD conversion values were obtained after 5h of treatment regardless of the value of this parameter. An analysis of the biodegradability of this type of effluent demonstrated the beneficial effect of the chemical pre-oxidation. According to the experimental results, it is suggested that there is an inhibitory effect of the wastewater due to its COD content and nature rather than attributable to the presence of high amounts of sodium chloride. Biodegradation efficiency increased as temperature was raised up to 30 degrees C. A further increase of this parameter up to 40 degrees C resulted in the death of the microorganisms.

TiO2 and Fe (III) photocatalytic ozonation processes of a mixture of emergent contaminants of water.

A mixture of three emergent contaminants: testosterone (TST), bisphenol A (BPA) and acetaminophen (AAP) has been treated with different photocatalytic oxidation systems. Homogeneous catalysts as Fe(III) alone or complexed with oxalate or citrate ions, heterogeneous catalysts as titania, and oxidants such as hydrogen peroxide and/or ozone have been used to constitute the oxidation systems. For the radiation type, black light lamps mainly emitting at 365 nm have been used. The effects of pH (3 and 6.5) have been investigated due to the importance of this variable both in ozone and Fe(III) systems. Removal of initial compounds and mineralization (total organic carbon: TOC) were followed among other parameters. For the initial compounds removal ozonation alone, in many cases, allows the highest elimination rates, regardless of the presence or absence of UVA light and catalyst. For mineralization, however, ozone photocatalytic processes clearly leads to the highest oxidation rates.