0000000000884957
AUTHOR
G. Camera-roda
A Dialysis Photocatalytic Reactor for the Green Production of Vanillin
In the present work, dialysis was used to recover vanillin while being produced by partial photocatalytic oxidation of ferulic acid in an aqueous solution at ambient temperature. The relatively high value of the permeate flux through a dense polyether-block amide membrane allowed continuously extracting vanillin from the reacting solution, thus avoiding its successive oxidation. The rate of vanillin formation was improved, compared to other reactor configurations, because intermediate compounds permeated from the reacting solution and did not hinder the reaction, while ferulic acid permeated in the opposite direction to partially replenish the reactor with the substrate. The photocatalytic …
Process intensification in a photocatalytic membrane reactor: Analysis of the techniques to integrate reaction and separation
Abstract Different methods to integrate reaction and separation in a membrane reactor are studied in the present work, with the aim being to highlight the pros and cons of the different alternatives and the effects of the intervening parameters. The coupling of the two processes can take place inside a single apparatus or using separate units. If a single apparatus is utilized, the coupling is more direct, but separate units offer higher degrees of freedom for the design with more opportunities to optimize the system without constraints. However, when using separate units, the integration of the two unit operations depends largely on the parameters intervening in the coupling procedure. The…
Photocatalytic ozonation: Maximization of the reaction rate and control of undesired by-products
Abstract In the so-called photocatalytic ozonation (PO) synergistic effects between photocatalysis and ozonation enhance the rate of oxidation of organic compounds, therefore this integrated process is very promising for use in water treatment. In the present work, it is demonstrated that the improvement that can be obtained by the integrated process in comparison with the uncoupled processes depends on the relative weight between photocatalysis and ozonation. In this respect, it has been found that a relatively low rate of photocatalysis (0.3 times the rate of ozonation) is sufficient to get the highest synergy and to maximize the performances in the oxidation of formate, the adopted model…
Synthesis of vanillin in water by TiO2 photocatalysis
Abstract The photoproduction of vanillin is studied in aqueous medium starting from trans-ferulic acid, isoeugenol, eugenol or vanillyl alcohol by using both commercial and home prepared TiO2 samples as photocatalysts and batch Pyrex photoreactors. The photo-oxidation at room temperature of these compounds produces vanillin with a selectivity ranging from 1.4 to 21 mol% with respect to the converted substrate. An investigation on the intermediates was performed in the case of trans-ferulic acid; for this substrate the most important intermediates were homovanillic acid, vanillyl mandelic acid, trans-caffeic acid, formic acid, acetic acid, and oxalic acid. The carbon mass balance, including …
Photocatalytic ozonation for a sustainable aquaculture: A long-term test in a seawater aquarium
Abstract A long-term test at a laboratory scale with a closed system (a coral reef aquarium) has been carried out to study the potentialities of photocatalytic ozonation and photocatalysis for the removal of noxious organic compounds in recirculating systems (aquaria and recirculating aquaculture systems) working with a minimum make up of new water. Attention has been focused not only on the depuration capabilities but also on possible negative phenomena, some of which could become apparent only at long times. After having tuned the system by setting appropriate operating conditions and procedures, positive results were obtained. In particular, it was observed that the alternation of photoc…
Coupling of membrane and photocatalytic technologies for selective formation of high added value chemicals
Abstract This review presents a survey of some heterogeneous photocatalytic processes for the synthesis of high-value added compounds carried out in photocatalytic membrane reactors (PMRs). The two technologies can be easily integrated due to the similar conditions at which they usually operate. Furthermore, significant advantages derive from the coupling and in some cases also synergistic effects can be observed. These features have been highlighted for the photocatalytic syntheses reviewed along with engineering and design aspects investigated for some industrially relevant high-value added compounds. Notably, photocatalytic syntheses carried out in PMRs are still rare mainly because inte…
Heterogeneous photocatalysis: guidelines on experimental setup, catalyst characterization, interpretation, and assessment of reactivity
Soon after the publication of the first pioneering works on heterogeneous photocatalysis, the number of papers on this topic continuously increased. This intriguing field of research is very complex as it endows with an interdisciplinary overview that involves different aspects of chemistry, physics, material and environmental sciences. Even if photocatalytic applications in real processes are often difficult to be implemented and scaled-up, investigations at laboratory scale are easy to be performed, and in some cases they may give rise to misconceptions. For this reason, the present work aims to sum up most of the common experimental techniques and procedures generally used in heterogeneo…
Heterogeneous Photocatalysis and Photoelectrocatalysis: From Unselective Abatement of Noxious Species to Selective Production of High-Value Chemicals
Heterogeneous photocatalysis and photoelectrocatalysis have been considered as oxidation technologies to abate unselectively noxious species. This article focuses instead on the utilization of these methods for selective syntheses of organic molecules. Some promising reactions have been reported in the presence of various TiO2 samples and the important role played by the amorphous phase has been discussed. The low solubility of most of the organic compounds in water limits the utilization of photocatalysis. Dimethyl carbonate has been proposed as an alternative green organic solvent. The recovery of the products by coupling photocatalysis with pervaporation membrane technology seems to be a…
A reaction engineering approach to kinetic analysis of photocatalytic reactions in slurry systems
Abstract The knowledge of the rate equation is fundamental for the assessment of the activity of the photocatalytic material and for the study, design and optimization of photocatalytic reactors. In the case of photocatalytic reactions, the local volumetric rate of photon absorption (LVRPA) affects the reaction rate and its inherently uneven distribution within a “slurry” reactor makes complex a correct kinetic analysis. In the present work it is shown which are the critical aspects of the kinetic analysis in slurry reactors and how to carry out photocatalytic experiments to minimize the misinterpretations of the experimental results. In particular, the influence of the type of illumination…
Properties of titanium dioxide
"Properties of titanium dioxide" presents a survey of the main physicochemical properties of TiO2 upon which rely all of the applications of this material. Structures and morphologies of titanium dioxide have been taken into account, also in correlation with thermodynamic properties. Bulk and surface defectivity has been described in detail, because of its relevant consequences in terms of catalytic activity. The basic mechanisms of interaction between photons and TiO2 have been discussed on the basis of the optoelectronic features of the semiconductor. Finally, electrical, mechanical, and rheological properties of TiO2 have been presented.
Combination of ozonation and photocatalysis for purification of aqueous effluents containing formic acid as probe pollutant and bromide ion
The treatment by advanced oxidation processes (AOPs) of waters contaminated by organic pollutants and containing also innocuous bromide ions may generate bromate ions as a co-product. In the present work heterogeneous photocatalysis and ozonation have individually been applied and in combination (integrated process) to degrade the organic compounds in water containing also bromide anions. The results show that: i) the sole photocatalysis does not produce bromate ions and in the case of its presence, it is able to reduce bromate to innocuous bromide ions; ii) the integration of photocatalysis and ozonation synergistically enhances the oxidation capabilities; and iii) in the integrated proces…
Photocatalytic process intensification by coupling with pervaporation
The integration of photocatalysis with a membrane separation process, in particular pervaporation, permits the recovery of valuable intermediate compounds (aromatic aldehydes) while they are produced avoiding their further degradation in the reactive ambient. In this way the yield and the conversion are enhanced. The coupling of the two processes is straightforward and the integration is complete even maintaining pervaporation and photocatalysis in two separate apparatuses provided that the process stream is continuously recycled at a sufficiently high flow rate. Additional advantages are: higher degree of purification of the aldehyde in the powder-free product stream, semicontinuous produc…
Green Synthesis of Vanillin: Pervaporation and Dialysis for Process Intensification in a Membrane Reactor.
In the present work, two different membrane processes (pervaporation and dialysis) are compared in view of their utilization in a membrane reactor, where vanillin, which is probably the most important aroma of the food industry, is synthesized in a green and sustainable way. The utilized precursor (ferulic acid, which is possibly a natural product from agricultural wastes) is partially oxidized (photocatalytically or biologically) and the product is continuously recovered from the reacting solution by the membrane process to avoid its degradation. It is observed that pervaporation is much more selective towards vanillin than dialysis, but the permeate flux of dialysis is much higher. Furthe…
Improvement of membrane performances to enhance the yield of vanillin in a pervaporation reactor.
In membrane reactors, the interaction of reaction and membrane separation can be exploited to achieve a “process intensification”, a key objective of sustainable development. In the present work, the properties that the membrane must have to obtain this result in a pervaporation reactor are analyzed and discussed. Then, the methods to enhance these properties are investigated for the photocatalytic synthesis of vanillin, which represents a case where the recovery from the reactor of vanillin by means of pervaporation while it is produced allows a substantial improvement of the yield, since its further oxidation is thus prevented. To this end, the phenomena that control the permeation of bot…
Pervaporation membrane reactors
Pervaporation is a peculiar membrane separation process which is now considered for the integration with some types of reactions in new promising and interesting applications. Indeed, pervaporation membrane reactors are suitable to some specific utilizations also in sustainable chemistry, which is an area currently characterized by a growing interest. The fundamentals of this type of membrane reactors are presented and the advantages and the difficulties in many applications are discussed and reviewed with particular attention to the opportunities for future developments.
A PERVAPORATION PHOTOCATALYTIC REACTOR FOR THE GREEN SYNTHESIS OF VANILLIN
Abstract Pervaporation is the ideal membrane separation process to be coupled with photocatalysis for the green synthesis of vanillin from ferulic acid. In fact the operative conditions of the two processes are absolutely congruent and the integration is straightforward even operating with separate equipments. The utilization of a highly selective membrane allows the continuous recovery of vanillin by pervaporation from the reacting solution, so that its oxidative degradation is largely avoided and the yield is substantially enhanced. The effects of the main parameters are analyzed resorting to a mathematical model, which is validated by a comparison with the experimental data. In particula…
PMRs Utilizing Non–Pressure-Driven Membrane Techniques
In the present chapter it is shown how photocatalytic membrane reactors utilizing membrane processes, which are not pressure driven, can exploit various mechanisms to obtain a substantial improvement of the process. The fundamentals of this particular type of membrane reactors are reviewed including the effects of the most important parameters and the methods and rules of coupling photocatalysis and membrane separation. The survey of the studies on photocatalytic membrane reactors (PMRs) utilizing pervaporation, dialysis, membrane contactors and membrane distillation offers the opportunity of discussing the advantages with respect to PMRs adopting pressure driven membrane processes. Indeed,…
Heterogeneous photocatalysis: a promising advanced oxidation process
This chapter reports the fundamentals of heterogeneous PC. In particular, different kinetic models and the influence of some parameters (such as pH, temperature, light intensity) on the rate of PC are described, and the effects of some photocatalyst modifications are discussed. Methods for photoreactor modeling are analyzed and the coupling of PC with other AOPs using H2O2, O3, and peroxydisulfate are discussed.
Guidelines for the assessment of the rate law of slurry photocatalytic reactions
Abstract The assessment of the rate law of slurry photocatalytic reactions appears to be a hard task, mainly because in this type of reactions the average rate of reaction, which is experimentally observed in a real reactor, could be very different from the “true” (intrinsic) rate of reaction, which cannot be measured directly. In the present work, it is shown how a proper mathematical model allows the utilization of the differential and/or the integral methods of kinetic analysis. The mathematical model must take into account not only the momentum and the mass balances, but also the radiative transfer equation. However, the discrimination among different proposed kinetic laws remains diffi…
Three-Dimensional Calibration for Routine Analyses of Bromide and Nitrate Ions as Indicators of Groundwater Quality in Coastal Territories
Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at d…
Features and application of coupled cold plasma and photocatalysis processes for decontamination of water
Dielectric barrier discharge plasma and photocatalysis have been proposed as tools for decontamination of process water, especially in food industry. The present investigation aims to redefine and identify the features of coupling the two technologies in terms of degradation efficiency of a model compound. Results show that, when the process is carried out in plasma activated water in the presence of irradiated TiO2, the efficiency of the integrated process is lower than the sum of the two processes acting separately. It is proposed that afterglow species, e.g. hydrogen peroxide and/or peroxynitrites could be activated by UVA light irradiation producing hydroxyl radicals in the liquid phase…