Photocatalytic valorization of biobased alcoholic wastes: a sustainable approach for the generation of green products

Ces dernières années, une attention croissante a été portée à la valorisation de différents types de résidus en produits chimiques à valeur ajoutée. La valorisation des résidus peut non seulement résoudre les problèmes environnementaux croissants et actuels, mais elle peut contribuer également au développement durable de la société. Les résidus alcooliques constituent une catégorie à fort potentiel de valorisation en différents types de produits chimiques. Dans ce contexte, la valorisation photocatalytique des résidus alcooliques est une approche prometteuse du point de vue du développement durable. L'objectif principal de la thèse était d'étudier la valorisation photocatalytique de différents résidus alcooliques biosourcés en produits à valeur ajoutée. À cet égard, ces travaux ont principalement porté sur (i) l'analyse des effets individuels et d'interaction des paramètres opératoires et l'optimisation de la production d'hydrogène à partir de glycérol (ii) l'étude de la cinétique de la production d'hydrogène à partir de glycérol et d'éthanol, (iii) la mise au point de catalyseurs nanocomposites au TiO2 utilisant des biomatériaux à base de carbone (nanotubes de carbone et sphères de carbone) pour la production d'hydrogène à partir de glycérol, et (iv) l'étude du mécanisme et de la cinétique de la valorisation photocatalytique du cyclohexanol en cyclohexanone. Pour la production d’hydrogène à partir du glycérol, les modèles « Réseau de neurones artificiels » ainsi que « Méthode des surfaces de réponses » ont été utilisés pour évaluer l’effet et l’importance des principaux paramètres opératoires (pourcentage de glycérol, catalyseur, et Pt (co-catalyseur), ainsi que pH). La comparaison de ces modèles a révélé une meilleure précision du premier, qui a été par la suite sélectionnée pour une optimisation basée sur un algorithme génétique. La plus grande quantité d'hydrogène produite s'est révélée être à 50% de glycérol dans l'eau (v/v), à une masse de catalyseur de 3,9 g/L, à 3,1% de Pt et à un pH de 4,5. Finalement, une analyse basée sur la méthode de Garson pour évaluer l’importance relative des paramètres opératoires a montré que les pourcentages de glycérol et de catalyseur affectent de façon différente la production d’hydrogène. L'effet des plus importants paramètres opératoires (catalyst loading, glycerol%, intensité de la lumière, and temps) sur la valorisation photocatalytique du glycérol en hydrogène a été analysé et un modèle cinétique a été développé sur la base d'un mécanisme proposé. La capacité du modèle à prédire le taux de production d'hydrogène pour différents substrats, photocatalyseurs et paramètres opératoires a été confirmée en comparant les valeurs calculées avec des données expérimentales de la littérature. Le rôle des composants carbonés (CT) biosourcées en tant que matrice, cocatalyseur et adsorbant dans les composites TiO2@CT a été étudié en utilisant des nanotubes de carbone et des sphères de carbone. L'analyse morphologique a permis d'examiner le rôle de la matrice et d’évaluer la formation uniforme du TiO2 sur le CT. Les expériences photocatalytiques ont été ensuite utilisées pour analyser les rôles du co-catalyseur et de l'adsorbant. Fait intéressant, les résultats ont révélé que l’incorporation de CNT dans un composite de TiO2 pouvait presque doubler le taux de production d’hydrogène (i) en l’absence de Pt ou (ii) à faible concentration en glycérol. Par conséquent, il a été constaté qu’en plus d’être une matrice, le CNT peut jouer deux autres rôles importants, comme co-catalyseur et adsorbant. Pour évaluer la valorisation des résidus alcooliques en produits liquides à valeur ajoutée, la conversion photocatalytique sélective du cyclohexanol en cyclohexanone a été investiguée par des études cinétiques et spectroscopiques. Un mécanisme de réaction a été proposé sur la base des résultats de l'analyse in situ ATR-FTIR et un modèle cinétique a été développé pour prédire le taux de production de cyclohexanone. Une très grande sélectivité de la cyclohexanone a été confirmée à la fois par des analyses spectroscopiques que chromatographiques (HPLC et GC-MS), démontrant que l'approche photocatalytique est une alternative prometteuse pour la production sélective de cyclohexanone. En résumé, les résultats de cette thèse ont montré que la photocatalyse est une alternative prometteuse pour la valorisation des résidus alcooliques biosourcés en produits à valeur ajouté. La conversion photocatalytique de ces résidus peut conduire à la production d'hydrogène comme carburant vert prometteur pour l'avenir. D'autre part, la photocatalyse peut être appliquee pour produire des composes liquides avec une sélectivité élevée.In the recent years, increasing attention has been paid to valorizing different types of waste materials to valuable chemicals. Waste valorization not only reduces the growing modern environmental issues, but also contributes to the sustainable development of the society. The alcoholic waste is an important category with high potential to be valorized into different types of valuable chemicals. As example, glycerol is a substantial alcoholic waste of biodiesel production process whose generation increased significantly during the recent years. In this context, photocatalytic valorization of alcoholic wastes is a promising approach from a sustainable development point of view. The main objective of the thesis was to study the photocatalytic valorization of different biobased alcoholic wastes to value-added products. In this regard, this work focused on (i) analyzing individual and interaction effect of operating parameters and optimization of hydrogen production from glycerol (ii) studying the kinetics of hydrogen production from glycerol and ethanol, (iii) developing TiO2 nanocomposite catalysts using biobased carbonaceous materials (carbon nanotubes and carbon spheres) and studding the roles of carbonaceous materials in hydrogen production from glycerol, and (iv) investigating the mechanism and kinetics of the photocatalytic valorization of cyclohexanol to cyclohexanone. For hydrogen production from glycerol, Artificial Neural Network (ANN) as well as Response Surface Methodology (RSM) models were employed to evaluate the effect and importance of the main operating parameters (glycerol%, catalyst loading, Pt (cocatalyst)%, and pH). Comparison of these models revealed that the ANN model had a better accuracy and it was therefore selected for a Genetic Algorithm-based optimization. The highest amount of hydrogen production was found to be at 50% glycerol in water (v/v), 3.9 g/L catalyst loading, 3.1% Pt, and pH of 4.5. Finally, a Garson’s method-based analysis of the relative importance of the operating parameters showed that the glycerol% and catalyst loading are, respectively, the least and most influential parameters on hydrogen production. The important operating parameters (catalyst loading, substrate%, light intensity, and time) of the process of photocatalytic valorization of glycerol and ethanol to hydrogen were analyzed and a kinetic model was developed based on a proposed mechanism. The ability of the model to predict the rate of hydrogen production for different substrates, photocatalysts, and ranges of operating parameters was confirmed by comparing the model predictions with the experimental data from literature. Carbon nanotube (CNT) and carbon sphere (CS) were used to prepare carbonaceous TiO2 composites and then the role of these biobased carbonaceous materials (CT) as template, cocatalyst, and adsorbent was investigated. The morphology analysis helped in examination of the template role and find the uniformity of the formed TiO2 on the template. On the other hand, the photocatalytic experiments assisted in the analysis of the cocatalyst and adsorbent roles of CT. Interestingly, the results revealed that CNT incorporation in TiO2 composite can almost double the rate of hydrogen production (i) in the absence of Pt or (ii) at low glycerol concentrations. Consequently, it was found that in addition to being a template, the CNT can play two important roles as cocatalyst and adsorbent. To evaluate the valorization of alcoholic wastes to valuable liquid product, photocatalytic selective conversion of cyclohexanol to cyclohexanone was analyzed kinetically and spectroscopically. A reaction mechanism was proposed based on the in-situ ATR-FTIR analysis results and a kinetic model was developed to predict the rate of cyclohexanone production. Experimental data were used to evaluate the kinetic parameters using genetic algorithm method and confirm the accuracy of model predictions. A very high selectivity of cyclohexanone was confirmed by both spectroscopic and chromatographic (HPLC and GCMS) analyses, demonstrating that the photocatalytic approach is a promising alternative for selective production of cyclohexanone. In summary, the results of this thesis showed that photocatalysis is a promising alternative for valorization of biobased alcoholic wastes to value-added products. Photocatalytic conversion of alcoholic wastes can lead to the production of hydrogen as a promising green fuel for the future. On the other hand, the conversion of alcoholic wastes can be engineered to produce valuable liquid product with high selectivity

Effects of water and basin depths in single basin solar stills: an experimental and theoretical study

The effects of water depth in solar stills were studied in many earlier works. It was revealed that in the previous experimental works, the water surface-cover distance (WCD) was altered with the change of the water depth. However, in this research, the effects of water depth and WCD were investigated separately, and effects of water depth on the performance of solar stills with the same WCD were examined for the first time. In this way at first, some experiments were conducted in the summer and winter seasons using the stills with the same water depths, but different basin depths (i.e. different WCDs). It was found that WCD can affect the amount of distillate yield up to 26%. Thus, it was concluded that to study the effect of water depth accurately, different stills should be employed at the same time (to keep WCD constant). In the second step, some experiments were conducted using four stills in the summer, fall and winter seasons to examine the effects of water depth, while the WCD was constant. In addition, the stills with different water depths were modeled analytically and their performance was investigated. Moreover, an empirical relationship was obtained between the distillate yield and the water depth. By comparing the results of this empirical relation with previous studies, it was revealed that the past researches reported a lower dependency (in the average 15%) of the distillate yield on the water depth, since in their experimental works, WCD was changed along with the water depth

Theoretical and experimental investigation on internal reflectors in a single-slope solar still

This study investigated the effect of an internal reflector (IR) on the productivity of a single-slope solar still (during the summer and winter) experimentally and theoretically. A mathematical model was presented which took into account the effect of all walls (north, south, west and east) of the still on the amount of received solar radiation to brine, and the model was validated with the experimental data. The model can calculate the yield of the still with and without IR on various walls. The results show that the simultaneous use of IR on front and side walls enhances the still’s efficiency by 18%. However, installation of an IR on the back wall can increase the annual efficiency by 22%. The installation of IRs on all walls in comparison to a still without IR can increase the distillate production at winter, summer and the entire year by 65%, 22% and 34%, respectively. Furthermore, the effect of cloud factor on the installation of IRs on all walls was examined, and the results indicate that the increasing the cloud factor decreases the influence of IRs significantly

A novel analytical performance investigation of varying water depth in an active multi-stage basin solar still in addition to optimization of water depth in a single stage basin still

In the present research, active solar basin stills are studied and the effect of water depth on output productivity is evaluated analytically. In order to validate the reliability of the results of the proposed model, they have been compared with the available Karimi’s experimental data with an acceptable accuracy. Then, the temperature distribution of the basin, covers, the water in the basin and heat transfer coefficients between the water as well as covers in all stages are calculated. Then, the amount of fresh water as an output are derived for one and multistage units. With increasing the number of stages from one to four, the amount of fresh water was increased by 42%, 72% and 94%, respectively. In addition, the amount of yield water for the ratio of three stages to two stages and four stages to three stages was increased 20% and 13%, respectively. Moreover, in this article, a new approach is adapted based on the variation of water depth instead of considering it constant and because of this methodology, there is an optimum value for water depth, which leads to the maximum productivity. Due to the storage of energy in water as a function of water depth, with an increase in the amount of water in the basin of solar stills more than the optimum value, or even decreasing the water depth below the optimum value, one should expect to get the basin without water at the end of day. This may lead to have less fresh water in the output at the end of the day. Finally, a correlation has been provided to calculate the productivity of a single basin still based on the water depth in the basin

Current developments in the chemical upcycling of waste plastics using alternative energy sources

The management of plastics waste is one of the most urgent and significant global problems now. Historically, waste plastics have been predominantly discarded, mechanically recycled, or incinerated for energy production. However, these approaches typically relied on thermal processes like conventional pyrolysis, which are energy-intensive and unsustainable. In this Minireview, we discuss some of the latest advances and future trends in the chemical upcycling of waste plastics by photocatalytic, electrolytic, and microwave-assisted pyrolysis processes as more environmentally-friendly alternatives to conventional thermal reactions. We highlight how the transformation of different types of plastics waste by exploiting alternative energy sources can generate value-added products such as fuels (H2 and other carbon-containing small molecules), chemical feedstocks, and newly functionalized polymers, which can contribute to a more sustainable and circular economy.Agency for Science, Technology and Research (A*STAR)Ministry of Education (MOE)National Research Foundation (NRF)Accepted versionH.S.S. acknowledges that this project is supported by A*STAR under the AME IRG grants A2083c0050, A1783c0003, and A1783c0002. H.S.S. is also grateful for the Singapore Ministry of Education Academic Research Fund Tier 1 grant RT 05/19. H.S.S. and X.Y.K. acknowledge that this research is supported by the Singapore National Academy of Science (SNAS) and the National Research Foundation (NRF) Singapore under its SNAS ASEAN Postdoctoral Fellowship (NRF-MP-2020-0001) program

Selective photocatalytic oxidation of cyclohexanol to cyclohexanone: A spectroscopic and kinetic study

In this work, spectroscopic and kinetic studies were performed on photocatalytic oxidation of cyclohexanol to cyclohexanone. The photocatalytic experiments were performed according to a three-level full factorial design and the rate of cyclohexanone production was determined by HPLC analysis. In situ ATR-FTIR analysis of the photocatalytic reaction revealed that cyclohexanol can be selectively converted to cyclohexanone, without the formation of significant amounts of carbonates and carboxylates. A reaction mechanism based on different steps from charge separation to cyclohexanone molecule formation is proposed. The results were utilized to determine the kinetic parameters (with the help of genetic algorithm) and validate the model. The developed kinetic model illustrates that the rate of cyclohexanone production increases as a power function with respect to the light intensity and decreases as an exponential function with respect to time. An excellent selectivity of cyclohexanone was confirmed by spectroscopic and chromatographic studies. This study demonstrates that photocatalysis can be a promising technology for formation of cyclohexanone from cyclohexanol

Metal-Supported TiO₂/SiO₂ Core-Shell Nanosphere Photocatalyst for Efficient Sunlight-Driven Methanol Degradation

The development of novel and active photocatalysts to industrialize photocatalysis technology is still a challenging task. In this work, a novel method is presented to prepare TiO2/SiO2 NSs by covering SiO2 nanospheres (NSs) with titanate-nanodiscs (TNDs) followed by calcination. In this regard, SiO2 NSs are first synthesized and then TNDs are deposited on the SiO2 NSs using a layer-by-layer deposition technique. The morphology of the prepared samples is analyzed via SEM and TEM analyses before and after the deposition. The analysis of metal (Cu, Pt, and Ni) loading on calcined TNDs/SiO2 NSs reveals the highest specific surface area (109 m2/g), absorption wavelength extension (up to 420 nm), and photocatalytic activity for the Cu-loaded sample. In addition, studying the effect of metal content shows that loading 3% Cu leads to the highest photocatalytic activity. Finally, it is demonstrated that H2S treatment can improve the photocatalytic activity by around 15%. These findings suggest the calcined TNDs/SiO2 NSs are a versatile photocatalyst with potential applications in other processes such as hydrogen production and CO2 valorization