ChemEngineering

This paper presents and patents new profiled- and annular-channel tangential swirlers with 1.8–3 times less hydraulic drag coefficient compared to swirlers with straight channel walls at the same flow rate, respectively. The results of numerical simulation of the gas velocity and pressure profiles for tangential swirler channels of different structures are presented. The modelling was carried out with the help of OpenFOAM software using the k-ε turbulence model. It is found that the shape of the velocity profile at the channel inlet has a decisive influence on the swirler drag coefficient. The greatest contribution to the total drag coefficient of the tangential swirler is made by the pressure drop at the channel inlet compared to the pressure drop at the channel wall and the channel outlet. The experimental dependencies of the tangential swirlers’ drag coefficient on the Reynolds number with a gas criterion of 2000–20,000 and the following structural channel parameters: width 1, 2–9 mm, height 1, 5–10 mm, number 5–45 units, inclination angle 0–45° are presented. The experimental data were compared with the modelling calculations and the convergence of data was achieved. The generalized dependence for the measurement of the hydraulic drag coefficient of three types of tangential swirlers considering the effect made by the geometric parameters (flow rate, width and height of the channel, wall inclination angle) on the pressure drop has been determined; it can be useful at the unit design stage as it allows for reducing the calculation time of the swirler parameters. Full article

The 21st century arrived with global growth of energy demand caused by population and standard of living increases. In this context, a suitable alternative to produce COx-free H₂ is the catalytic decomposition of methane (CDM), which also allows for obtaining high-value-added carbonaceous nanomaterials (CNMs), such as carbon nanotubes (CNTs). This work presents the results obtained in the co-production of CO_x-free hydrogen and CNTs by CDM using Ni–Cu and Co–Cu catalysts supported on carbon derived from Argan (Argania spinosa) shell (ArDC). The results show that the operation at 900 °C and a feed-ratio CH₄:H₂ = 2 with the Ni–Cu/ArDC catalyst is the most active, producing 3.7 g_C/g_metal after 2 h of reaction (equivalent to average hydrogen productivity of 0.61 g H₂/g_metal∙h). The lower productivity of the Co–Cu/ArDC catalyst (1.4 g_C/g_metal) could be caused by the higher proportion of small metallic NPs (<5 nm) that remain confined inside the micropores of the carbonaceous support, hindering the formation and growth of the CNTs. The TEM and Raman results indicate that the Co–Cu catalyst is able to selectively produce CNTs of high quality at temperatures below 850 °C, attaining the best results at 800 °C. The results obtained in this work also show the elevated potential of Argan residues, as a representative of other lignocellulosic raw materials, in the development of carbonaceous materials and nanomaterials of high added-value. Full article

Combustible carbon-based energy is still prevailing as the world’s leading energy due to its high energy density. However, the oxidation of these hydrocarbons disturbs the natural carbon cycle greatly by increasing greenhouse gases. As emission legislation becomes more rigorous, lean premixed combustion becomes promising because it can reduce nitrogen oxides (NOx) and Carbon Monoxide (CO) emissions without compromising efficiency. However, utilising lean premixed flames in industrial combustors is not easy because of its thermo-acoustic instabilities associated with pressure fluctuations and the non-linearity in the mean reaction rate. Therefore, reliable predictive combustion models are required to predict emissions with sensible computational costs to use the mode efficiently in designing environmentally friendly combustion systems. Along with the promising methodologies capable of modelling turbulent premixed flames with low computational costs is the ERN-RANS framework. Thus, this study aims to compute a bluff-body stabilised premixed flames close to blow-Off using the ERN-RANS framework. As a result, a satisfactory agreement is reached between the predicted and measured values. Full article

The synthesis and applications of composites based on layered double hydroxides (LDHs) and nanocarbons have recently seen great development. On the one hand, LDHs are versatile 2D compounds that present a plethora of applications, from medicine to energy conversion, environmental remediation, and heterogeneous catalysis. On the other, nanocarbons present unique physical and chemical properties owing to their low-dimensional structure and sp² hybridization of carbon atoms, which endows them with excellent charge carrier mobility, outstanding mechanical strength, and high thermal conductivity. Many reviews described the applications of LDH/nanocarbon composites in the areas of energy and photo- and electro-catalysis, but there is still scarce literature on their latest applications as heterogeneous catalysts in chemical synthesis and conversion, which is the object of this review. First, the properties of the LDHs and of the different types of carbon materials involved as building blocks of the composites are summarized. Then, the synthesis methods of the composites are described, emphasizing the parameters allowing their properties to be controlled. This highlights their great adaptability and easier implementation. Afterwards, the application of LDH/carbon composites as catalysts for C–C bond formation, higher alcohol synthesis (HAS), oxidation, and hydrogenation reactions is reported and discussed in depth. Full article

Carbon dioxide is a byproduct of our industrial society. It is released into the atmosphere, which has an adverse effect on the environment. Carbon dioxide management is necessary to limit the global average temperature increase to 1.5 degrees Celsius and mitigate the effects of climate change, as outlined in the Paris Agreement. To accomplish this objective realistically, the emissions gap must be closed by 2030. Additionally, 10–20 Gt of CO₂ per year must be removed from the atmosphere within the next century, necessitating large-scale carbon management strategies. The present procedures and technologies for CO₂ carbonation, including direct and indirect carbonation and certain industrial instances, have been explored in length. This paper highlights novel technologies to capture CO₂, convert it to other valuable products, and permanently remove it from the atmosphere. Additionally, the constraints and difficulties associated with carbon mineralization have been discussed. These techniques may permanently remove the CO₂ emitted due to industrial society, which has an unfavorable influence on the environment, from the atmosphere. These technologies create solutions for both climate change and economic development. Full article

Photocatalytic hydrogen production was studied with a formic acid solution with titanium dioxide (TiO₂) with the aid of simultaneous Rh deposition. The optimum conditions were as follows: Rh loading, 0.1 wt%; formic acid concentration, 1.0%; solution, pH 2.2; temperature, 50 °C. Under the optimum conditions, the photocatalytic hydrogen production with TiO₂ by the simultaneous deposition of Rh was 5.0 mmol g⁻¹, 12.2 mmol g⁻¹ and 16.0 mmol g⁻¹ after 1 h, 3 h and 5 h of irradiation time for black light, respectively. Rh/TiO₂ photocatalysts were characterized by XRD, SEM, photoluminescence spectra, diffuse reflectance spectra and the BET surface area. The reaction mechanism of photocatalytic hydrogen production from formic acid by Rh/TiO₂ was also proposed. Full article

In an attempt to evaluate the separation of certain impurities that arise in some stages of the production of cyclohexanone, this work analyzed the possibility of removing five of these substances via rectification. Due to the scarcity of experimental vapor–liquid equilibrium data for most of the solutions in the effluent of the global process, prior knowledge of their behavior is required. In this work, two predictive models, UNIFAC and COSMO-RS, were used to determine a priori the possibility of obtaining, by distillation, the individual components of seven of the binaries formed by the combination of these five compounds. Since both procedures described quasi-ideal behavior for all the chosen solutions, the results are considered as an approximation, owing to the special nature of the studied systems. The results and characteristics of each system are discussed separately. Full article

The analysis of the corrosion phenomenon of the installations of the largest refinery in Romania confirmed the existence of its conditions, in the atmospheric distillation plants of crude oil, in the heat exchangers, and in the petrol and diesel hydrofining plants. However, the slightest effect of this phenomenon was found in the dome, the plates, and the exhaust pipes at the top of the distillation column, as well as in the reflux vessel of the atmospheric distillation plant. The main cause of the corrosion phenomenon and the increase in the corrosion areas of the material of the crude oil refining installations is the presence of hydrochloric acid, obtained after incorrect desalination (hydrolysis of calcium and magnesium chloride). To prevent this phenomenon, in laboratory conditions, we tested an antacid inhibitor (alkyl phenol) and a residual product (undistilled polyamine), with the role of supplementing the commercial inhibitor with a cheap product. The effectiveness of these additives was evaluated by introducing specimens made from the material taken from the refining column and from the reflux vessel into a solution of hydrochloric acid of various concentrations (5–15%). This solution was treated with the two corrosion inhibitors, the analysis of their effectiveness being performed at concentrations ranging between 0.05 and 0.2%. In addition, in this article, we deduced the equations of variation of the corrosion rate, depending on the working temperature of the refinery. Full article

Biofuels production become a target for many researchers nowadays. Biodiesel is one the most important biofuels that are produced from biomass using economics and modern techniques. The ductile cast iron solid waste dust is one of the wastes produced by the cast iron industry which has a bad effect on the environment. This paper investigates the possibility of reusing ductile cast iron solid waste as a biodiesel heterogeneous catalyst used in its production from sunflower waste cooking oil. Four reaction parameters were chosen to determine their effect on the reaction responses. The reaction parameters are M:O ratio, reaction time and temperature, and catalyst loading. The reaction responses are the biodiesel and glycerol conversions. The upper and lower limits are selected for each reaction parameter such as (50–70 °C) reaction temperature, (5–20) methanol to oil molar ratio, (1–5%) catalyst loading, and (1–4 h) reaction time. Optimization was done with economic and environmental targets which include lowering the biodiesel production cost, increasing the volume of biodiesel produced, and decreasing the amount of resulting glycerol. The optimum reactions are 20:1 M:O molar ratio, 65 °C reaction temperature, 5 wt% catalyst loading, 2 h reaction time, and a stirring rate of 750 rpm. The biodiesel conversion resulting at this optimum reaction conditions is 91.7 percent with agreed with all biodiesel standards. The catalyst usability test was done it was found the catalyst can be used up to 4 times after that a fresh catalyst is required to be used. Full article

The steam reforming of ethanol, methanol, and other oxygenates (e.g., bio-oil and olive mill wastewater) using Ni-based catalysts have been studied by the scientific community in the last few years. This process is already well studied over the last years, being the critical point, at this moment, the choice of a suitable catalyst. The utilization of these oxygenates for the production of “green” H₂ is an interesting alternative to fuel fossils. For this application, Ni-based catalysts have been extensively studied since they are highly active and cheaper than noble metal-based materials. In this review, a comparison of several Ni-based catalysts reported in the literature for the different above-mentioned reactions is carried out. This study aims to understand if such catalysts demonstrate enough catalytic activity/stability for application in steam reforming of the oxygenated compounds and which preparation methods are most adequate to obtain these materials. In summary, it aims to provide insights into the performances reached and point out the best way to get better and improved catalysts for such applications (which depends on the feedstock used). Full article

In this work, a set of novel fluorinated ionic liquids (FILs), based on different tetra-alkyl-phosphonium cations with perfluorobutanesulfonate and perfluoropentanoate anions, were synthesized and characterized in order to check their suitability to apply as engineering solvents. Thermophysical and thermal properties were both determined between 293.15 and 353.15 K, and the molecular volumes and free volumes and the coefficients of isobaric thermal expansion were determined from experimental values of refractive index and density. Lastly, the Walden plot was used to evaluate the ionicity of the novel FILs. The cytotoxicity of these compounds was also determined using the human hepatocellular carcinoma cells (HepG2) and the human colon carcinoma cells (Caco-2). Finally, the results were all discussed with the aim of understanding the behaviour of these compounds, considering the influence of the anion and the hydrogenated alkyl chain length. In summary, the new FILs synthesized in this work present adequate properties for their application in different industrial processes. Most of these compounds are liquid at room temperature with high decomposition temperatures. All phosphonium-based FILs have lower densities than conventional ionic liquids and common organic solvents, and the viscosity depends directly on the selected anion. Furthermore, the ionicity of FILs based on the sulfonate anion is higher than those based on the carboxylate anion. Finally, the phosphonium-based FILs have no significant effect on cellular viability at lower concentrations. Full article

The present study provides and examines an experimental and CFD simulation to predict and accurately quantify the individual phase holdup. The experimental findings demonstrated that the increase of solid beads has a significant influence on the (U_mf), as comparatively small glass beads particles require a low (U_mf) value, which tends to increase as the diameter of the beads increases. Besides that, the expansion ratio is proportional to the velocity of the liquid. Even though, the relationship becomes inversely proportional to the diameter of the beads. The liquid holdup was found to increase with increasing liquid velocity, however, the solid holdup decreased. The Eulerian–Eulerian granular multiphase flow technique was used to predict the overall performance of the liquid–solid fluidized beds (LSFBs). There was a good agreement between the experimental results and the dynamic properties of liquid–solid flows obtained from the CFD simulation, which will facilitate future simulation studies of liquid–solid fluidized beds. This work has further improved the understanding and knowledge of CFD simulation of such a system at different parameters. Furthermore, understanding the hydrodynamics features within the two-phase fluidization bed, as well as knowing the specific features, is essential for good system design, enabling the systems to perform more effectively. Full article

In this study, the poisoning effects of cerium oxide (${\mathrm{CeO}}_2$) as the contaminant on the performance of proton exchange membrane fuel cells (PEMFCs) are evaluated. An experimental setup was developed to analyze the performance characteristic (I-V) curves in contaminated and non-contaminated conditions. Focused ion-beam scanning electron microscopy (FIB-SEM) cross-section images were obtained as an input for the energy dispersive X-ray (EDX) analysis. The results of the EDX analysis verified the presence of ${\mathrm{CeO}}_2$ in the contaminated membrane electrode assembly (MEA), in addition to fluorine and sulfur. EDX analysis also revealed that as a result of ${\mathrm{CeO}}_2$ contamination, sulfur and fluorine would be distributed all around the MEA, instead of being only in the membrane. The results illustrate that hydrofluoric acid (HF), sulfuric acid (${\mathrm{H}}_2{\mathrm{SO}}_4$), and fluorinated polymer fragments are released, which enhance the crossover of the reactant gases through the membrane, hence reducing the cell’s performance. The I-V characteristic curves proved that the non-contaminated PEMFC setup had double the performance of the contaminated PEMFC. Full article

This study was focused on the simultaneous organosolv treatment/extraction of waste orange peels (WOP) for the effective recovery of polyphenolic antioxidants. The treatments were performed with aqueous glycerol mixtures, which were acidified either with citric acid or hydrochloric acid (HCl). Process optimization was carried out using response surface methodology and comparative appraisal of the different processes tested, based on both the extraction efficiency factor (F_EE), severity factor (SF) or combined severity factor (CSF). Metabolite stability was also of major concern, and it was examined by deploying liquid chromatography-mass spectrometry. The results drawn suggested 90% (w/w) glycerol to be the highest-performing system, providing a yield in total polyphenols of 44.09 ± 5.46 mg GAE g⁻¹ DM at 140 °C for 50 min, with a F_EE of 2.20 and an SF of 2.88. Acidification with 1% citric acid was proven less efficient and equally severe, whereas acidification with 1% HCl was less severe but also less efficient. The major disadvantage associated with the use of HCl was its detrimental impact on the polyphenolic composition of WOP since major metabolites, such as narirutin, hesperidin and didymin, did not survive the process. By contrast, the formation of lower molecular weight compounds was observed. With regard to antioxidant properties, the extract obtained with aqueous glycerol displayed significantly higher antiradical activity and reducing power, which was in line with its higher concentration in total polyphenols. It was concluded that organosolv treatment with aqueous glycerol under the conditions employed may boost polyphenol recovery from WOP, thus giving extracts with powerful antioxidant characteristics. Full article

Consumers’ interest in a high-quality healthy diet is creating a growing trend in the food industry, focusing on the design and development of new products rich in bioactive compounds. This work involves the formulation of a vegetable sauce obtained from a mixture of pumpkin and pepper, the study of the evolution of bioactive compounds, quality and sensory parameters during storage at 4 and 25 °C, the influence of the packaging materials (PVC, PE/PA, and PS), and the migration degree. Antioxidant activity, polyphenols, carotenoids, and brown pigments contents were studied at 25 °C. Overall migration of the containers and the evolution of the physicochemical parameters and sensory attributes of the sauce were analyzed. All plastic materials showed an overall migration lower than the limit of EU and Mercosur Regulations. PVC better preserved polyphenols, antioxidant activity, and carotenoids until 50, 10, and 30 days, respectively, and lower development of brown pigments was observed. Higher storage temperatures favored undesirable changes in sensory attributes before 50 days of storage. PVC can be used to achieve greater conservation of the sensory attributes of sauce, regardless of the storage temperature. It could be considered the best material to preserve the bioactive properties and sensory attributes of the sauce until 30 days. Full article

Novel materials with a periodic structure have recently been intensively studied for various photonic and photocatalytic applications due to an efficient light harvesting ability. Here, inverse opal titania (IOT) has been investigated for possible enhancement of photocatalytic activity. The IOT films were prepared on a glass support from silica and polystyrene (PS) opals by sandwich-vacuum-assisted infiltration and co-assembly methods, respectively. The reference sample was prepared by the same method (the latter) but with PS particles of different sizes, and thus without photonic feature. The modification of preparation conditions was performed to prepare the films with a high quality and different photonic properties, i.e., photonic bandgap (PBG) and slow photons’ wavelengths. The morphology and optical properties were characterized by scanning electron microscopy (SEM) and UV/vis spectroscopy, respectively. The photocatalytic activity was evaluated (also in dependence on the irradiation angle) for oxidative decomposition of acetaldehyde gas under irradiation with blue LED by measuring the rate of evolved carbon dioxide (CO₂). It has been found that PBG wavelength depends on the size of particles forming opal, the void diameter of IOT, and irradiation angle, as expected from Bragg’s law. The highest activity (more than two-fold enhancement in the comparison to the reference) has been achieved for the IOT sample of 226-nm void diameter and PBG wavelengths at 403 nm, prepared from almost monodisperse PS particles of 252-nm diameter. Interestingly, significant decrease in activity (five times lower than reference) has been obtained for the IOT sample of also high quality but with 195-nm voids, and thus PBG at 375 nm (prohibited light). Accordingly, it has been proposed that the perfect tunning of photonic properties (here the blue-edge slow-photon effect) with bandgap energy of photocatalyst (e.g., absorption of anatase) results in the improved photocatalytic performance. Full article

Heat and power cogeneration plants based on fuel cells are interesting systems for energy- conversion at low environmental impact. Various fuel cells have been proposed, of which proton-exchange membrane fuel cells (PEMFC) and solid oxide fuel cells (SOFC) are the most frequently used. However, experimental testing rigs are expensive, and the development of commercial systems is time consuming if based on fully experimental activities. Furthermore, tight control of the operation of fuel cells is compulsory to avoid damage, and such control must be based on accurate models, able to predict cell behaviour and prevent stresses and shutdown. Additionally, when used for mobile applications, intrinsically dynamic operation is needed. Some selected examples of steady-state, dynamic and fluid-dynamic modelling of different types of fuel cells are here proposed, mainly dealing with PEMFC and SOFC types. The general ideas behind the thermodynamic, kinetic and transport description are discussed, with some examples of models derived for single cells, stacks and integrated power cogeneration units. This review can be considered an introductory picture of the modelling methods for these devices, to underline the different approaches and the key aspects to be taken into account. Examples of different scales and multi-scale modelling are also provided. Full article

A rapid, facile, and environmentally benign strategy to electrochemical oxidation of metallic tungsten under pulse alternating current in an aqueous electrolyte solution was reported. Particle size, morphology, and electronic structure of the obtained WO₃ nanopowders showed strong dependence on electrolyte composition (nitric, sulfuric, and oxalic acid). The use of oxalic acid as an electrolyte provides a gram-scale synthesis of WO₃ nanopowders with tungsten electrochemical oxidation rate of up to 0.31 g·cm⁻²·h⁻¹ that is much higher compared to the strong acids. The materials were examined as photoanodes in photoelectrochemical reforming of organic substances under solar light. WO₃ synthesized in oxalic acid is shown to exhibit excellent activity towards the photoelectrochemical reforming of glucose and ethylene glycol, with photocurrents that are nearly equal to those achieved in the presence of simple alcohol such as ethanol. This work demonstrates the promise of pulse alternating current electrosynthesis in oxalic acid as an efficient and sustainable method to produce WO₃ nanopowders for photoelectrochemical applications. Full article

The potential for barium sulphate nanoparticles to be used in a variety of important fields has sparked a lot of attention. Methods for obtaining this material by milling (top-down approach) are not very popular due to the difficulty of controlling the size and shape of particles, as well as changes in their physicochemical properties during milling. More promising is the bottom-up approach, which is the interaction of Ba²⁺ and SO₄²⁻ ions in a liquid environment. Direct precipitation is the simplest method; however, it does not allow control of the particle size. Microemulsions, microreactors membrane dispersion, as well as spinning disc reactors are used to overcome drawbacks of direct precipitation and allow control of particle size and shape. This is ensured mainly by intensive controlled micromixing of the precursors with concentrations close to saturated ones. The present review focuses on recent advances in the production of barium sulfate nanoparticles using various approaches, as well as their advantages and limitations. The issues of scaling up the techniques are also considered, and promising methods for obtaining BaSO₄ nanoparticles are also discussed. Full article