Band 20, Heft 1 - Special Issue: In Honour of Dr. Orlando M. Alfano; Guest Editors: María de los Milagros Ballari and Benito Serrano Rosales

The current work studies a novel and affordable methodology to estimate and quantify the photon flux absorbed and the amount of light that leaves from an illuminated photocatalytic system with TiO 2 suspended in water. To achieve it, a new parameter B F S λ w a t $BF{S}_{\lambda }^{wat}$ is defined and presented. It indicates, for every wavelength, the fraction of the incoming radiation which is not absorbed by the system. B F S λ w a t $BF{S}_{\lambda }^{wat}$ was estimated by means of actinometric experiments in a jacketed reactor and a model based on Beer–Lambert law. For wavelengths below 388 nm and TiO 2 concentrations between 0.05 and 2 g L −1 , experimental values of B F S λ w a t $BF{S}_{\lambda }^{wat}$ were between 0.77 and 0.27. In the second part of the work, a simple kinetic model, which breaks down the effect of incident radiation and kinetic constant, is developed. For this, the photon flux absorbed by TiO 2 , previously determined, was included in the model. This new model was tested in the photocatalytic degradation of 2,4-dichlorophenol under different TiO 2 concentrations. The kinetic model fits satisfactorily the experimental values and a new kinetic constant k ʹ ap [mol·L −1  Einstein −1 ] was obtained, which is independent of the amount of catalyst loaded to the system. This achievement may be very useful for an easy initial comparison, design or scaling up of different photocatalytic reactors with similar geometry.

Nickel on alumina support offers opportunity for gasification of biomass for hydrogen production. In a recent contribution from our research team, (González Castañeda, D. G., et al. 2019) showed that cerium or lanthanum co-impregnation at 2 wt% with nickel may have a favorable effect for biomass catalytic gasification. However, and given an observed influence of lanthanum on the formation of small Ni crystallite sizes, five Ni/γ-Al 2 O 3 based fluidizable La promoted catalysts were studied. Nickel-alumina catalysts promotion was effected varying La in the 0.5 and 1.0 wt% range. Once impregnation precursors loaded, they were reduced at 480 °C via an activation step. Catalysts were characterized using BET, XRD, AA, TPR, TPD, H 2 -chemisorption, TEM-EDX and FTIR. Catalyst performance was established in a fluidized CREC Riser Simulator, using: a) glucose as surrogate biomass, b) 600 °C, c) steam/biomass (S/B) ratio of 1, d) catalyst /biomass (C/B) ratio of 3.2 and e) 20 s reaction time. Data obtained was analyzed using an ANOVA statistical data analysis package with the 5 wt% Ni and 0.5–1 wt% La and Ce on γ-Al 2 O 3 catalysts, prepared using a pH of 1 of impregnating solution were the best yielding 0.53–0.56 hydrogen molar fractions. These catalysts also gave a 39% reduced coke, and this while compared with the coke formed on the 2% Ce – 5 wt%Ni/γ-Al 2 O 3 (González Castañeda, D. G., et al. 2019). This promising performance was assigned to the dominant NH 3 -TPD medium acidity, the high catalyst specific surface (∼140 m 2 /g), and the good 9% metal dispersion with 9–10 nm nickel crystallites.

This manuscript presents a simplified analysis for estimating anisotropic, non-homogeneous extinction coefficients in porous solids as a function of the pore morphology and size distribution. The model contains two main simplifications: (1) the pore network consists of hollow interspersed spheres and cylinders, and (2) each surface exchanges radiation (through diffuse emission) only with itself and adjacent surfaces. The model yields photon flight length (PFL) probability distribution functions (PDFs), describing Beerian and non-Beerian anisotropic extinction processes. The method is three orders of magnitude faster than the Monte Carlo Ray Tracing Method (MCRT), yielding Root Mean Square Errors between 0 and 35% for the PFL–PDFs and 0–25% for the anisotropic extinction coefficients. Finally, this work presents a local geometric criterium determining whether the model applies to some given area of the porous solid, so it remains useful even when not applicable to the whole domain.

The influence of Al 2 O 3 –ZrO 2 and TiO 2 –ZrO 2 supports on NiMo-supported catalysts at a different sulfur concentration in a model hydrodeoxygenation (HDO)-hydrodesulfurization (HDS) co-processing reaction has been studied in this work. A competition effect between phenol and dibenzothiophene (DBT) for active sites was evidenced. The competence for the active sites between phenol and DBT was measured by comparison of the initial reaction rate and selectivity at two sulfur concentrations (200 and 500 ppm S). NiMo/TiO 2 –ZrO 2 was almost four-fold more active in phenol HDO co-processed with DBT than NiMo/Al 2 O 3 –ZrO 2 catalyst. Consequently, more labile active sites are present on NiMo/TiO 2 –ZrO 2 than in NiMo/Al 2 O 3 –ZrO 2 confirmed by the decrease in co-processing competition for the active sites between phenol and DBT. DBT molecules react at hydrogenolysis sites (edge and rim) preferentially so that phenol reacts at hydrogenation sites (edge and edge). However, the hydrogenated capacity would be lost when the sulfur content was increased. In general, both catalysts showed similar functionalities but different degrees of competition according to the highly active NiMoS phase availability. TiO 2 –ZrO 2 as the support provided weaker metal-support interaction than Al 2 O 3 –ZrO 2 , generating a larger fraction of easily reducible octahedrally coordinated Mo- and Ni-oxide species, causing that NiMo/TiO 2 –ZrO 2 generated precursors of MoS 2 crystallites with a longer length and stacking but with a higher degree of Ni-promotion than NiMo/Al 2 O 3 –ZrO 2 catalyst.

This manuscript analyzes the suitability of a recently proposed numerical method, the First-Order Scattering Method (FOS), to describe radiation transfer in a Solar Compound Parabolic Collector Photoreactor (CPCP). The study considers five different irradiance conditions ranging from fully diffuse to fully direct solar radiation, with 90 and 45° angled rays. Three photocatalysts at different loadings were considered: Evonik P25, Graphene Oxide, and Goethite, selected due to (1) their relevance in photocatalytic applications and (2) the availability of optical transport properties in the open literature. The study shows that the method is efficient and free of statistical noise, while its accuracy is not affected by the boundary condition’s complexity. The method’s accuracy is very high for photocatalysts with low to moderate albedos, such as Goethite and Graphene Oxide, displaying Normalized Absoluted Mean Error below 3%, i.e., comparable to the Monte Carlo (MC) Method’s statistical fluctuations.

The study of the best experimental conditions and catalyst for the hydrogenation (HYD) of light cycle oil (LCO) for upgrading purposes was carried out. The objective was to examine the ability of two commercial hydrotreatment (HDT) catalysts for selective aromatic saturation. The effect of the hydrotreatment operation parameters (temperature, pressure, liquid hourly space velocity, H 2 /HC ratio) on the sulfur and nitrogen contents and in the saturation of aromatic hydrocarbons was also investigated. The goal was to obtain the highest conversion to mono-aromatic hydrocarbons from this di-aromatic (naphthalene derivatives) type feedstock, and at the same time to get reasonable hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) performance to avoid contaminant hydrocarbons for the next step (usually hydrocracking, HCK). An appropriate hydrotreated product with the highest concentration of mono-aromatic derivatives, a minimum reduction on the total aromatic content, and suitable decrements of sulfur and nitrogen compounds, was achieved using a cobalt-molybdenum supported on alumina catalyst, at 330 °C, 5.5 MPa, and a liquid hourly space velocity of 1.1 h −1 . Additionally, the kinetics of the HDA was studied, assuming a lump characterization into tri-, di- and mono-aromatic and aliphatic hydrocarbons, pseudo-first-order reaction rates between these conversions, and thermal losses and diffusional resistances to be undetectable.

The simultaneous processes of diffusion, adsorption and chemical reaction, considering the transient nature of the concentration profiles in the porous catalyst particles as applied to the analysis of consecutive reactions A → B → C , where reactant and products are subjected to diffusion limitations, are analyzed. The concentrations of the desired intermediate product B , both the average in the catalytic particles and the observed in the fluid phase, initially increase as a function of time until reaching a maximum value and then decline due to the consumption in the secondary reaction. Due to the diffusion restrictions and the adsorption effect, the observed selectivities, calculated from the concentrations in the fluid phase, are always lower than the true selectivities, which also include the amounts accumulated in the particles. Besides depending on the rates of the primary and secondary reactions, the observed yield of product B also depends on the system adsorption capacity, i.e., the relationship between the capacities of the particles and the external fluid phase to accumulate the reactant species. For a given relationship between the intrinsic rates of the primary and secondary reactions, the higher the system adsorption capacity, the lower the observed yield of B as a function of conversion. The relationship between the observed yield of B and the observed conversion of A , calculated considering the transient state of the concentration profiles in the particles, is coincident with that predicted by classical models, which assume the steady state in the particles, when the system adsorption capacity is extremely small.

The utilization of titanium dioxide (TiO 2 ) photocatalysis for water and air purification is a frequently used method due to TiO 2 having properties making it chemically inert, highly cost-effective, abundant, non-toxic, and environmentally-friendly. In an effort to increase the efficiency of the degradation process, an in-depth understanding of the effects of the structure and number of thin film coatings is needed. Transparent, anatase-form titanium dioxide thin films were prepared via the sol-gel method and deposited onto microscopic glass slides using a novel spraying technique , with coatings ranging from 1 to 10. Characterization of the TiO 2 thin film coated slides was performed using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The contribution shows that the coating technique is efficient in covering important areas of the surface and that it is suitable for a multiple coating layers thin film. The SEM imagines show that the surface of the slides increase coverage as the number of layers increases. This is potentially suitable for a mechanized spraying approach to upscaling the production of thin films for advanced oxidation applications.

Among the large family of emergent pharmaceutical contaminants, we find acetaminophen (ACE) that critically needs to be removed from wastewater. Advanced Oxidation Process (AOP) have proven effective in the degradation of large molecular contaminants from water. To the best of our knowledge this is the first study reported on the degradation of ACE based on immobilized TiO 2 thin films. In an effort to increase the understanding of the efficiency of the degradation process, an in-depth investigation of the effects of the structure, i.e., coating layers and the amount of surface, i.e., number of coated slides used, is needed. Transparent, anatase-form TiO 2 thin films were prepared via the sol-gel method (Rawal, S., S. Buer, J. R. Sanders, and P. E. Arce. 2021. “Photocatalytic Degradation of Acetaminophen from Water Solutions Via Thin Films. Part I: Synthesis and Characterization of TiO 2 Thin Films.” International Journal of Reactor Engineering [Accepted]) and deposited onto glass microscope slides using a novel spraying technique, with coatings ranging from one to 10 layers. This contribution summarizes the effect of several key factors including initial concentration of the ACE, the number of coating layers (6, 8, and 10) on the glass slides and the number (4 and 6) of slides on the degradation levels for three selected media, e.g., acid, neutral and base. Comparisons studies, supported by statistical analysis between two different sets (4 and 6) of slides with discussion of potential physical-chemical reasons behind the behaviors are reported. Finally, global, first order kinetic rate constants are also reported for the different conditions used in the investigation. Although further research would be needed, in general the results are promising for the potential degradation of ACE in continuous flow systems by using immobilized TiO 2 on surfaces as thin films.

The effect of Co into the titanium oxide matrix as photocatalysts in the generation of hydrogen from water is herein reported. Ti–Co mixed oxides and pure titania were synthetized by sol-gel. The Co content was 0, 1, 3, 5, and 10 wt.%. The solids were characterized by Scanning electron microscope-energy dispersive spectrometer (SEM-EDS), N 2 physisorption, X-ray difrraction (XRD), ultraviolet visible spectroscopy (UV–Vis), spectroscopy Raman, X-ray photoelectron spectroscopy (XPS) spectroscopy and High resolution transmission electron microscope (HRTEM). The results showed that the mixed oxides show larger specific surface areas (73–186 m 2 /g) compare to that of pure TiO 2 (64 m 2 /g). The XRD patterns of the Ti-Co samples resemble that of anatase and segregation of Co was not observed by this technique. The band gap energies of these solids vary from 3.05 to 2.85 eV which are smaller than that of pure TiO 2 (3.2 eV). The Ti-Co oxides showed an enhancement in the hydrogen production (∼3056 μmol/h) compare to that of TiO 2 (190 μmol/h) when using UV light. Furthermore, the photocatalytic activity of titania (110 μmol/h) for this reaction was also smaller than those observed for the Ti-Co mixed oxides (∼4056 μmol/h) under visible light.