Rodica Stanescu

Laboratory-scale photomineralisation of n-alkanes in aqueous solution, by photocatalytic membranes immobilising titanium dioxide

Kinetics of photocatalytic oxidation of methane, ethane, n-heptane, n-decane, and n-dodecane, to yield intermediates, and photomineralisation of intermediates, to yield carbon dioxide and water, was studied in aqueous solution, by a laboratory-scale photoreactor and photocatalytic membranes immobilizing 30±3 wt.% of TiO2, in the presence of stoichiometric hydrogen peroxide as oxygen donor. The whole volume of irradiated solution was 4.000±0.005 L, the ratio between this volume and the geometrical apparent surface of the irradiated side of the photocatalytic membrane was 3.8±0.1 cm, and the absorbed power 0.30W/cm (cylindrical geometry). A kinetic model was used, by which mineralisation of substrate to CO2 was supposed to occur, by kinetic constants k1, through one single intermediate, mediating the behaviour of all the numerous real intermediates formed in the path from the substrate to CO2 (kinetic constants of formation of the latter being k2). A competitive Langmuirian adsorption of both substrate and “intermediate” was also supposed to be operative, as expressed by apparent adsorption constants k1 and k2, possessing a, partly at least, kinetic significance. By Langmuir-Hinshelwood treatment of initial rate data, starting values of the k and K couples were obtained, from which, by a set of differential equations, the final optimised parameters, k1 and k1, k2 and K2, were calculated, able fit the whole photomineralisation curve, and not only its initial segment, as the Langmuirian parameters do. The parameters of present work are critically compared with those obtained in two preceding set of studies relative to n-alkanoic acids and to n-alkanols. They are interpreted on the basis of a closer behaviour of hydrocarbons to alkanols, from the photocatalytic point of view, than to carboxylic acids are. Discussion of limiting effective quantum yields, and their comparison with maximum, theoretical values, are also carried out.

Laboratory-scale photomineralization of n-alkanes in gaseous phase by photocatalytic membranes immobilizing titanium dioxide

Kinetics of photocatalytic oxidation of methane, ethane, and n-heptane, to yield intermediates, and photomineralization of intermediates, to yield carbon dioxide and water, was studied in the gaseous phase, at 308±2 K, by a laboratory-scale photoreactor and photocatalytic membranes immobilizing 30±3 wt.% of TiO2, in the presence of aerosolized stoichiometric hydrogen peroxide as oxygen donor, and at a relative humidity close to 100%. The whole volume of irradiated solution was 4.000±0.005 L, the ratio between this volume and the geometrical apparent surface of the irradiated side of the photocatalytic membrane was 3.8±0.1 cm, and the absorbed power was 0.30 W/cm (cylindrical geometry). The pinetic parameters of the present work substantially coincide with those of the same molecules previously studied in aqueous solution, within the limits of experimental uncertainty. Photocatalytic processes thus appear to be controlled by interface phenomena, which are ruled kinetically, and apparently also thermodynamically, by concentration gradients, independently on diffusion and other processes in the aqueous or gaseous bulk, if turbulence in these phases is adequately assured.

Solar energy driven photocatalytic membrane modules for water reuse in agricultural and food industries. Pre-industrial experience using s-triazines as model molecules

A membrane module, utilizing photocatalytic membranes, has been employed in a pilot plant, in conditions of solar irradiation, to investigate photomineralisation of atrazine, propazine, terbutylazine, symazine, prometryn, and ametryn, as model molecules of s-triazine herbicides, at a standard concentration (1.0 ppm) simulating those of contaminated aquifers, by using ozone as oxygen supplier. Photocatalytic composite membranes immobilised 30 ± 3w t.% of TiO2 and 6 wt.% of a synergic mixture of tri-(t-butyl)- and tri-(i-propyl)vanadate(V). Photomineralisation was followed by analysis of substrate disappearance, as such, and by total organic carbon (TOC) analysis. A four parameters kinetic model was employed, as set up in previous studies of this series, to interpret the whole photomineralisation curve. Quantum yields, as indicative of catalytic and photocatalytic mechanisms, were evaluated satisfactorily: they are discussed, and compared with those of previous studies on the same substrates, carried out in the same module, but in conditions of practically monochromatic irradiation (254 nm) within the range of optical absorption of semiconductor. Finally, in order to compare effectiveness of composite photocatalytic membranes, described above, prepared by photografting, either in the presence or in the absence of an added photopromoter, as well as that of metallic membranes, onto which the semiconductor without any photopromoter was present as a 3-4 µm thick surface layer, directly produced on the nanotechnologically treated surface, with those of other commercial materials, parallel experiments were carried out, by using commercial sheets in which the semiconductor was immobilised, by a method based substantially on glueing by colloidal silica. All of these comparison experiments were carried out at a laboratory scale, by using, in these experiments, dioxygen of air, or ozone as oxygen donors.

Influence of Irradiance, Flow Rate, Reactor Geometry, and Photopromoter Concentration in Mineralization Kinetics of Methane in Air and in Aqueous Solutions by Photocatalytic Membranes Immobilizing Titanium Dioxide

Photomineralization of methane in air (10.0–1000 ppm (mass/volume) of C) at 100% relative humidity (dioxygen as oxygen donor) was systematically studied at 318±3 K in an annular laboratory-scale reactor by photocatalytic membranes immobilizing titanium dioxide as a function of substrate concentration, absorbed power per unit length of membrane, reactor geometry, and concentration of a proprietary vanadium alkoxide as photopromoter. Kinetics of both substrate disappearance, to yield intermediates, and total organic carbon (TOC) disappearance, to yield carbon dioxide, were followed. At a fixed value of irradiance (0.30 W⋅cm−1), the mineralization experiments in gaseous phase were repeated as a function of flow rate (4–400 m3⋅h−1). Moreover, at a standard flow rate of 300 m3⋅h−1, the ratio between the overall reaction volume and the length of the membrane was varied, substantially by varying the volume of reservoir, from and to which circulation of gaseous stream took place. Photomineralization of methane in aqueous solutions was also studied, in the same annular reactor and in the same conditions, but in a concentration range of 0.8–2.0 ppm of C, and by using stoichiometric hydrogen peroxide as an oxygen donor. A kinetic model was employed, from which, by a set of differential equations, four final optimised parameters, 𝑘1 and 𝐾1, 𝑘2 and 𝐾2, were calculated, which is able to fit the whole kinetic profile adequately. The influence of irradiance on 𝑘1 and 𝑘2, as well as of flow rate on 𝐾1 and 𝐾2, is rationalized. The influence of reactor geometry on 𝑘 values is discussed in view of standardization procedures of photocatalytic experiments. Modeling of quantum yields, as a function of substrate concentration and irradiance, as well as of concentration of photopromoter, was carried out very satisfactorily. Kinetics of hydroxyl radicals reacting between themselves, leading to hydrogen peroxide, other than with substrate or intermediates leading to mineralization, were considered, and it is paralleled by a second competition kinetics involving superoxide radical anion.

Nonlinear Modelling of Kinetic Data Obtained from Photocatalytic Mineralisation of 2,4-Dichlorophenol on a Titanium Dioxide Membrane

Photomineralisation of 2,4-dichlorophenol (DCP) in aqueous solutions (10.0–100.0 mg/L of C) was systematically studied at K, in an annular laboratory-scale reactor, by photocatalytic membranes immobilizing titanium dioxide, as a function of substrate concentration, and absorbed power per unit length of membrane. Kinetics of both substrate disappearance, to yield intermediates, and total organic carbon (TOC) disappearance, to yield carbon dioxide, were followed (first series of experiments). At a fixed value of irradiance (1.50 Wc), other series of mineralization experiments were repeated (second series of experiments) by carrying out only analyses of chemical oxygen demand (COD), in order to compare modelling results of the two sets of experiments. In both sets of experiments, stoichiometric hydrogen peroxide was used as oxygen donor. For the first series of experiments, a kinetic model was employed, already validated in previous work, from which, by a set of differential equations, four final optimised parameters, and , and , were calculated. By these parameters, the whole kinetic profile could be fitted adequately. The influence of irradiance on and could be rationalised very well by this four-parameter kinetic model. Modelling of quantum yields, as a function of irradiance, could also be carried out satisfactorily. As has been found previously for other kinds of substrates, modelling of quantum yields for DCP mineralization is consistent with kinetics of hydroxyl radicals reacting between themselves, leading to hydrogen peroxide, other than with substrate or intermediates leading finally to carbon dioxide, paralleled by a second competition kinetics involving superoxide radical anion. For the second series of experiments, on the contrary, the Langmuir-Hinshelwood model was employed. Uncertainties of COD analyses, coupled with discrepancies of this model and with its inability to reproduce kinetics up to complete mineralization, are underlined.