Gianluca Li Puma

Preparation of titanium dioxide photocatalyst loaded onto activated carbon support using chemical vapor deposition: A review paper

Various methods to prepare and characterize TiO(2) photocatalyst loaded onto activated carbon (AC) support have been developed over the last decade. This photocatalyst has been used in a variety of investigations, i.e. from water decontamination to direct pollutant degradation in aqueous and gas phase systems using UV irradiation and lately with the assistance of ultrasonic sound waves. Chemical vapor deposition (CVD) method is one of the most promising and well-researched methods for deposition of catalysts onto supports. Given its advantage, from an engineering and fundamental aspect, CVD method also has commercial applications. A detailed search of published reports of these investigations was carried out and analyzed in this paper with focus on CVD techniques, activated carbon support and sonication.

Solar light-responsive Pt/CdS/TiO2 photocatalysts for hydrogen production and simultaneous degradation of inorganic or organic sacrificial agents in wastewater.

Photocatalytic degradation of waste material in aqueous solutions and simultaneous production of hydrogen was studied with the double purpose of environmental remediation and renewable energy production. Both powdered and immobilized Pt/CdS/TiO(2) photocatalysts were used to oxidize model inorganic (S(2-)/SO(3)(2-)) and organic (ethanol) sacrificial agents/pollutants in water. Powdered Pt/CdS/TiO(2) photocatalysts of variable CdS content (0-100%) were synthesized by precipitation of CdS nanoparticles on TiO(2) (Degussa P25) followed by deposition of Pt (0.5 wt %) and were characterized with BET, XRD, and DRS. Immobilized photocatalysts were deposited either on plain glass slides or on transparent conductive fluorine-doped SnO(2) electrodes. The results show that it is possible to produce hydrogen efficiently (20% quantum efficiency at 470 nm) by using simulated solar light and by photocatalytically consuming either inorganic or organic substances. CdS-rich photocatalysts are more efficient for the photodegradation of inorganics, while TiO(2)-rich materials are more effective for the photodegradation of organic substances.

Sonophotocatalysis in advanced oxidation process: A short review

Sonophotocatalysis involves the use of a combination of ultrasonic sound waves, ultraviolet radiation and a semiconductor photocatalyst to enhance a chemical reaction by the formation of free radicals in aqueous systems. Researchers have used sonophotocatalysis in a variety of investigations i.e. from water decontamination to direct pollutant degradation. This degradation process provides an excellent opportunity to reduce reaction time and the amount of reagents used without the need for extreme physical conditions. Given its advantages, the sonophotocatalysis process has a futuristic application from an engineering and fundamental aspect in commercial applications. A detailed search of published reports was done and analyzed in this paper with respect to sonication, photocatalysis and advanced oxidation processes.

Photocatalytic Mineralization of Commercial Herbicides in a Pilot-Scale Solar CPC Reactor: Photoreactor Modeling and Reaction Kinetics Constants Independent of Radiation Field

The six-flux absorption-scattering model (SFM) of the radiation field in the photoreactor, combined with reaction kinetics and fluid-dynamic models, has proved to be suitable to describe the degradation of water pollutants in heterogeneous photocatalytic reactors, combining simplicity and accuracy. In this study, the above approach was extended to model the photocatalytic mineralization of a commercial herbicides mixture (2,4-D, diuron, and ametryne used in Colombian sugar cane crops) in a solar, pilot-scale, compound parabolic collector (CPC) photoreactor using a slurry suspension of TiO(2). The ray-tracing technique was used jointly with the SFM to determine the direction of both the direct and diffuse solar photon fluxes and the spatial profile of the local volumetric rate of photon absorption (LVRPA) in the CPC reactor. Herbicides mineralization kinetics with explicit photon absorption effects were utilized to remove the dependence of the observed rate constants from the reactor geometry and radiation field in the photoreactor. The results showed that the overall model fitted the experimental data of herbicides mineralization in the solar CPC reactor satisfactorily for both cloudy and sunny days. Using the above approach kinetic parameters independent of the radiation field in the reactor can be estimated directly from the results of experiments carried out in a solar CPC reactor. The SFM combined with reaction kinetics and fluid-dynamic models proved to be a simple, but reliable model, for solar photocatalytic applications.

Modelling and design of thin-film slurry photocatalytic reactors for water purification

Abstract Photocatalytic oxidation processes are highly effective clean technologies for the degradation and mineralization of a wide variety of priority pollutants in water and wastewater. However, the application of heterogeneous photocatalysis for wastewater treatment on an industrial scale has been impeded by a lack of mathematical models that can be readily applied to reactor design and scale-up. As a results current photocatalytic reactors in research and development have been designed by empirical or semi-empirical methods only. In this paper, a simple and generic mathematical model for steady-state, continuous flow, thin-film, slurry (TFS) photocatalytic reactors for water purification using solar and UV lamps is presented. The model developed is applicable to TFS flat plate and annular photoreactors of (a) falling film design or (b) double-skin design, operating with three ideal flow conditions: (1) falling film laminar flow, (2) plug flow and (3) slit flow. The model is expressed in dimensionless form and scale-up of TFS photocatalytic reactors can be carried out by dimensional analysis. In addition, the model parameters can be estimated easily from real systems and model solutions can be obtained with little computational effort. Comparison of a number of ideal flow systems shows that both falling film laminar flow and plug flow operation modes give higher performance than the slit flow system. Slit flow operation mode results in lower conversions due to the non-correspondence of fluid-residence time and the transversal radiation field. The effect of optical thickness, on reactor performance and the evolution of radial profiles of a model pollutant with photoreactor length are presented for each of the operation modes. The falling film laminar flow system was found to be more efficient than the plug flow system when the reactor conversion is above 80%. For lower reactor conversion the plug flow system was found to be marginally more efficient than the falling film laminar flow system. A methodology for the optimal geometrical design of a highly efficient configuration of TFS photocatalytic reactors is also presented. The mathematical models presented may be used as a tool for the design, scale-up and optimization of these types of photocatalytic reactors.

Ozonation kinetics of winery wastewater in a pilot-scale bubble column reactor

The degradation of organic substances present in winery wastewater was studied in a pilot-scale, bubble column ozonation reactor. A steady reduction of chemical oxygen demand (COD) was observed under the action of ozone at the natural pH of the wastewater (pH 4). At alkaline and neutral pH the degradation rate was accelerated by the formation of radical species from the decomposition of ozone. Furthermore, the reaction of hydrogen peroxide (formed from natural organic matter in the wastewater) and ozone enhances the oxidation capacity of the ozonation process. The monitoring of pH, redox potential (ORP), UV absorbance (254 nm), polyphenol content and ozone consumption was correlated with the oxidation of the organic species in the water. The ozonation of winery wastewater in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modeled by the two-film theory of mass transfer and chemical reaction. It was determined that the ozonation reaction can develop both in and across different kinetic regimes: fast, moderate and slow, depending on the experimental conditions. The dynamic change of the rate coefficient estimated by the model was correlated with changes in the water composition and oxidant species.

Ozonation kinetics of cork-processing water in a bubble column reactor

The oxidative degradation of organic pollutants present in cork-processing water at natural pH (6.45) was studied in a bubble column ozonation reactor. A steady reduction in both chemical oxygen demand (COD) and total organic carbon (TOC) was observed under the action of ozone alone and the feasibility of deep mineralisation (organic matter removal more than 90% in 120 min under the following experimental conditions: liquid volume 9L; superficial gas velocity 6.8x10(-3) m s(-1); ozone partial pressure 1.31 kPa; initial COD 328 mg L(-1); initial TOC 127 mg L(-1)) was demonstrated. The monitoring of pH, redox potential (ORP) and the mean oxidation number of carbon (MOC) was correlated with the oxidation and mineralisation of the organic species in the water. The ozonation of cork-processing water in the bubble column was analysed in terms of a mole balance coupled with ozonation kinetics modelled by the two-film theory of mass transfer and chemical reaction. Under the experimental conditions used, and in contrast with the literature, it was determined that the reaction follows a fast kinetic regime at the beginning of the oxidation process, shifting to the moderate and the slow kinetic regimes at later stages of the oxidation reaction. The dynamic change of the rate coefficient estimated by the model was correlated to changes in the water composition.

A novel fountain photocatalytic reactor: model development and experimental validation

The application of photocatalysis for water treatment and purification on an industrial scale can be accelerated by the development of both new photoreactor designs and mathematical models. A novel, pilot-plant, thin-film, slurry photocatalytic reactor for water treatment and purification is presented in this paper. The reactor is a “fountain” photocatalytic reactor, consisting of a flattened water bell irradiated from above. Such a reactor configuration is particularly suitable for large-scale solar applications of photocatalysis. A dimensionless mathematical model for the fountain photocatalytic reactor is presented in this paper. The model was developed using parameters that can be estimated easily from real systems and model solutions can be obtained with little computational effort. The model was validated with experimental results from the photocatalytic oxidation of salicylic acid in a pilot-scale reactor using titanium dioxide (TiO2) as the photocatalyst. Experiments were performed under a number of different conditions by varying substrate concentration, intensity of the incident radiation, catalyst loading, flow rate, recycle ratio and water fountain diameter. The model results were found to fit the experimental data well in all cases. The modeling approach can be extended to other thin-film slurry photocatalytic reactors.

A laminar falling film slurry photocatalytic reactor. Part I—model development

Abstract The application of photocatalysis for wastewater treatment on an industrial scale has been partially impeded by the lack of simple mathematical models and optimisation studies. In this paper, a mathematical model (LSSE-LSPP model) for a laminar falling film slurry (LFFS) photocatalytic reactor is presented. The model is expressed in terms of five dimensionless parameters and can be solved with a minimal number of simple integrations. Model predictions are presented for different reaction kinetics and model parameters. As the parameters used in the model can be readily estimated from real systems, the model may be used for scale-up. A study of the sensitivity of the model to variations of the model parameters and validation of the model with experimental results of the oxidation of salicylic acid in a pilot-scale LFFS photocatalytic reactor are presented in Part II of this paper.

Mechanism and experimental study on the photocatalytic performance of Ag/AgCl @ chiral TiO2 nanofibers photocatalyst: the impact of wastewater components.

The effect of the water matrix components of a secondary effluent of a urban wastewater treatment plant on the photocatalytic activity of Ag/AgCl @ chiral TiO2 nanofibers and the undergoing reaction mechanisms were investigated. These effects were evaluated through the water components-induced changes on the net rate of hydroxyl radical (˙OH) generation and modeled using a relative rate technique. Dissolved organic matter DOM (k=-2.8×10(8) M(-1) s(-1)) scavenged reactive oxygen species, Cl(-) (k=-5.3×10(8) M(-1) s(-1)) accelerated the transformation from Ag to AgCl (which is not photocatalytically active under visible-light irradiation), while Ca(2+) at concentrations higher than 50 mM (k=-1.3×10(9) M(-1) s(-1)) induced aggregation of Ag/AgCl and thus all of them revealed inhibitory effects. In contrast, NO3(-) (k=6.9×10(8) M(-1) s(-1)) and CO3(2-) (k=3.7×10(8) M(-1) s(-1)) improved the photocatalytic activity of Ag/AgCl slightly by improving the rate of HO˙ generation. Other ubiquitous secondary effluent components including SO4(2-) (k=3.9×10(5) M(-1) s(-1)), NH3(+) (k=3.5×10(5) M(-1) s(-1)) and Na(+) (k=2.6×10(4) M(-1) s(-1)) had negligible effects. 90% of 17-α-ethynylestradiol (EE2) spiked in the secondary effluent was removed within 12 min, while the structure and size of Ag/AgCl @ chiral TiO2 nanofibers remained stable. This work may be helpful not only to uncover the photocatalytic mechanism of Ag/AgCl based photocatalyst but also to elucidate the transformation and transportation of Ag and AgCl in natural water.