ChemEngineering, Volume 6, Issue 4 (August 2022) – 20 articles

Aluminum from saline slags generated during the recycling of this metal, extracted under reflux conditions with aqueous NaOH, was used in the synthesis of hydrocalumite-type solids with the formula Ca₂Al_1–mFe_m(OH)₆Cl·2H₂O. The characterization of the obtained solids was carried out by powder X-ray diffraction, infrared spectroscopy, thermal analysis, element chemical analysis, N₂ adsorption-desorption at −196 °C and electron microscopy. The results showed the formation of Layered Double Hydroxide-type compounds whose characteristics varied as the amount of incorporated Fe³⁺ increased. These solids were calcined at 400 °C and evaluated for the catalytic photodegradation of ibuprofen, showing promising results in the elimination of this drug by advanced oxidation processes. The CaAl photocatalyst (without Fe) showed the best performance under UV light for the photodegradation of ibuprofen. Full article

This study presents an optimization strategy for recovery of oil from Japonica Luna rice bran using supercritical carbon dioxide (scCO₂), based on design of experiments (DoE). Initially, a 2⁴⁻¹ two level fractional factorial design (FFD) was used, and pressure, temperature, and scCO₂ flow rate were determined as the significant variables; while the yield, total flavonoids content (TFC), and total polyphenols content (TPC) were the response functions used to analyze the quality of the extracts recovered. Subsequently, central composite design (CCD) was applied to examine the effects of the significant variables on the responses and create quadratic surfaces that optimize the latter. The following values of pressure = 34.35 MPa, temperature = 339.5 K, and scCO₂ flow rate = 1.8 × 10⁻³ kg/min were found to simultaneously optimize the yield (6.83%), TPC (61.28 μmol GAE/g ext), and TFC (1696.8 μmol EC/g ext). The fatty acid profile of the oils was characterized by GC-FID. It was demonstrated that the acids in largest quantities are C16:0 (15–16%), C18:1 (41%), and C18:2 (38–39%). Finally, three mass transfer models were applied to determine the mass transfer coefficients and assess the cumulative extraction curves, with an AAD% of 4.16, for the best model. Full article

This study proposes a mathematical modeling approach for evaluating the effect of applying a permanent electric field on the biodegradation of 1,2-dibromoethane by bacterial cells of Bradyrhizobium japonicum 273. Two models for inhibited microbial growth including product inhibition were composed—one using the Monod–Yerusalimsky approach and another one—the Levenspiel kinetic equation. The models were used to process own experimental data obtained without an electric field and ones obtained at the application of an electric field. The experiments were carried out at an optimum anode potential of 0.8 V vs. the standard hydrogen electrode (SHE). Three initial concentrations of substrate were tested: 0.05, 0.1, and 0.15 g dm⁻³. The modeling takes into account the product inhibition on microbial growth assuming 2-bromoethanol as the first biodegradation product. It was found that the positive effect of the electric field is the enhancement of microbial growth, expressed by the increase in the maximum specific growth rate and the increase in the inhibition constant when the model of Monod–Yerusalimsky is applied. The main effect of the electric field is in the increase in the rate constant of 2-bromoethanol removal by electrochemical oxidation, enabling the enhancement the microbial growth and substrate conversion to the product. The obtained results show that the application of a permanent electric field leads to a higher electrochemical oxidation rate (with a rate constant up to 60% higher than for the control experiments) and complete substrate and 2-bromoethanol biodegradation. The model of Levenspiel is not so sensitive to the effects of the electric field on product inhibition. Full article

After subjecting Zamora building stones to accelerated ageing tests, colour changes were studied, namely: (a) freezing/thawing and thermal shock (gelifraction and thermoclasty), and (b) combination of freezing/thawing plus thermal shock and salt crystallisation (sulphates or phosphates) (gelifraction, thermoclasty and haloclasty). Zamora building stones are silicified conglomerates (silcretes) from the Cretaceous that show marked colour changes due to the remobilisation of iron oxyhydroxides. In this work, four varieties were: white stone; ochreous stone; white and red stone; and purple stone Their micromorphological characterization (skeleton, weathering plasma and porosity/cutan) is formed of grains and fragments of quartz and quartzite as well as by accesory minerals muscovite and feldspar (more or less altered), and some opaque. Quartz, feldspar and illite/mica were part of the skeleton; kaolinite, iron oxyhydroxides, and CT opal were part of the weathering plasma or cutans; their porosity were 11.7–8.7%. Their chromatic data have been statistically analysed (MANOVA-Biplot). They showed higher variations in ΔE*, ΔL*, Δa* and Δb*on combined freezing/thawing plus thermal shock and sulphates crystallisation leading to rapid alteration of the building stones. Chromatic differences between the other two artificial ageing tests were less evident and were not detected in all samples. The global effect of ageing on the Zamora building stones darkened them and reduced their yellowing. The ochreous stone suffered the least variation and the purple stone the most. This study of the colour by statistical analyse may be of interest for the evaluation and monitoring of stone decay, which is an inexpensive, simple, easy and non-destructive technique. Full article

Hydrotalcite is the name of a mineral discovered in Sweden in 1842 whose formula is Mg₆Al₂(OH)₁₆CO₃·4H₂O and presents a layered crystal structure that consists of positively charged hydroxide layers neutralized by interlayer anions as carbonate, also containing water molecules. The ease of their synthesis and the possibility of incorporating other layer cations and interlayer anions have made this type of layered double hydroxides (LDH) a group of very interesting materials for industry. In addition to LDH and due to the name of the most representative mineral, this group of compounds is commonly called hydrotalcite-like materials, or simply hydrotalcites. Another way of referring to them is as anionic clays because of their layered structure but, unlike classical clays, their layers are positive and their interlayers are anionic. The main fields of application of these solids comprise catalysis, catalyst support, anion scavengers, polymer stabilizers, drug carriers, or adsorbents. This paper briefly summarizes some of the work carried out by Professor Rives over more than thirty years, focused, among other topics, on the study of the synthesis, characterization, and applications of hydrotalcites. This research has led him to train many researchers, to collaborate with research groups around the world and to publish reference papers and books in this field. This contribution, written to be included in the Special Issue “A Themed Issue in Honor of Prof. Dr. Vicente Rives”, edited on the occasion of his retirement, only shows a small part of his scientific research and intends to value and recognize his cleverness and his enormous scientific and human quality. Full article

Rosmarinic acid (RA) is present in a broad variety of plants, including those in the Lamiaceae family, and has a wide range of pharmacological effects, particularly antioxidant activity. To extract RA from Orthosiphon stamineus (OS) leaves, a Lamiaceae plant, a suitable extraction process is necessary. The present study used a green extraction method of supercritical carbon dioxide (SCCO₂) extraction with the addition of ethanol as a modifier to objectively measure and correlate the solubility of RA from OS leaves. The solubility of RA in SCCO₂ was determined using a dynamic extraction approach, and the solubility data were correlated using three density-based semi-empirical models developed by Chrastil, del Valle-Aguilera, and Gonzalez. Temperatures of 40, 60, and 80 °C and pressures of 10, 20, and 30 MPa were used in the experiments. The maximum RA solubility was found at 80 °C and 10 MPa with 2.004 mg of rosmarinic acid/L solvent. The RA solubility data correlated strongly with the three semi-empirical models with less than 10% AARD. Furthermore, the fastest RA extraction rate of 0.0061 mg/g min⁻¹ was recorded at 80 °C and 10 MPa, and the correlation using the Patricelli model was in strong agreement with experimental results with less than 15% AARD. Full article

Development in the textile industry leads to an increased demand for the use of various dyes. Moreover, there is the use of some dyes in the food industry as well as medical diagnostics. Thereby, increased demand for dyes in various fields has resulted in dye-containing wastewater. Only a small portion of the generated wastewater is adequately treated. The rest is usually dumped or otherwise directly discharged into the sewage system, which ultimately enters rivers, lakes, and streams. The handling and disposal of such concentrated wastewater, especially the dye-containing wastewater, is considered to be a major environmental issue from the moment of its generation to its ultimate disposal. Conventional water treatment methods such as flotation, filtration, adsorption, etc., are non-destructive physical separation processes. They only transfer the pollutants to other phases, thereby generating concentrated deposits. The advanced oxidation process (AOP) is one of the most effective emerging methods for the treatment of wastewater containing chemical pollutants. The method involves the formation and interaction of highly reactive hydroxyl radicals under suitable activation conditions. These radicals are non-selective and efficient for the destruction and eventual mineralization of recalcitrant organic pollutants. This review aims at the pros and cons of using photocatalysis as an efficient AOP to degrade dye-containing wastewater. Full article

5-hydroxymethylfurfural (5-HMF) is an important platform molecule for the synthesis of high-added value products. Several synthesized clay materials, such as mesoporous hectorite and fluorohectorite, in addition to commercial montmorillonite K-10, have been acid modified by different methodologies to be applied as catalysts for the obtention of 5-HMF from glucose. The effects of the Brønsted and/or Lewis acidity, the reaction temperature and time, and the catalyst/glucose ratio on the conversion but especially on the selectivity to 5-HMF have been studied. By comparing the synthesized clays, the best selectivity to 5-HMF (36%) was obtained at 140 °C for 4 h with H-fluorohectorite because of the presence of strong Brønsted acid sites, although its conversion was the lowest (33%) due to its low amounts of Lewis acid sites. Different strategies, such as physical mixtures of montmorillonite K10, which contains high amounts of Lewis acid centers, with Amberlyst-15, which has high amounts of Brønsted acid sites, or the incorporation of rhenium compounds, were carried out. The best selectivity to 5-HMF (62%) was achieved with a mixture of 44 wt % Amberlyst-15 and 56 wt % of montmorillonite K10 for a 56% of conversion at 140 °C for 4 h. This proportion optimized the amount of Brønsted and Lewis acid sites in the catalyst under these reaction conditions. Full article

The Hill Equation and Hill Coefficient have been used extensively in biochemistry for the description of noncovalent binding. Previously, the Hill Coefficient was correlated with the Gibbs free energy, which suggests that the Hill Equation might be extensible to covalent binding phenomena. To evaluate this possibility, the Hill Equation was compared to the Debye Model and Einstein Solid in the calculation of heat capacity for 53 covalent solids, which included stainless steels and refractory ceramics. Hill Equation specific heat predictions showed a standard error of 0.37 J/(mole⋅Kelvin), whereas errors from the Debye Model and Einstein Solid were higher at 0.45 J/(mole⋅Kelvin) and 0.81 J/(mole⋅Kelvin), respectively. Furthermore, the Hill Equation is computationally efficient, a feature that can accelerate industrial chemical process simulation(s). Given its speed, simplicity, and accuracy, the Hill Equation likely offers an alternative means of specific heat calculation in chemical process models. Full article

In recent decades, the increasing use of pesticides to improve food productivity has led to the release of effluents that contaminate the environment. To prepare a material that may help to treat effluents generated during agricultural practice, we used a new method based on the non-hydrolytic sol-gel route to obtain zinc photocatalysts in aluminophosphate matrixes. IR spectroscopy, X-ray diffraction, thermal analysis, differential scanning electron microscopy, energy dispersion spectroscopy, and specific surface area and pore volume determined from the nitrogen adsorbed were used to characterize materials treated at different temperatures. X-ray analysis showed how heat-treatment affected the structure of the material: Zn-AlPO₄ in the trigonal and orthorhombic phase was obtained at 750 and 1000 °C, respectively. These phases directly influenced the ability of the material to generate OH radicals. The capacity of the materials to treat effluents was tested in the photodegradation of the pesticide Fipronil. The photocatalytic reactions were monitored by ultraviolet-visible spectroscopy and gas chromatography-mass spectrometry analyses. Zn-AlPO₄ treated at 750 °C showed better photodegradation results--it removed 80% of the pesticide in 2 h when higher mass (150 mg) was tested. Long-time treatment of the effluent with Zn-AlPO₄ treated at 750 °C completely photodegraded Fipronil. GC-MS analysis confirmed the photodegration profile, and only traces of Fipronil were observed after photocatalytic reaction for 120 min in the presence of Zn-AlPO₄ treated at 750 °C under UV radiation. Full article

Development of ceramic pigments with controlled particle sizes below 1 µm is essential for the preparation of ceramic inks used in inkjet digital decoration that is currently being applied in the ceramics sector. A black ceramic pigment based on NiCoCrFe composition has been prepared using thermal decomposition of hydrotalcite-like compounds. The stoichiometry ratio between different cations was studied to obtain the blackest pigment, giving Ni_0,5Co_0,5CrFeO₄ the better cation ratio, also the thermal treatment, comparing traditional firing in an electric furnace with microwave treatment. Samples have been characterized by X-ray diffraction, Scanning Electron Microscopy and Lab colour measurement. Microwave treatment showed the best way to obtain a pigment with spinel-type structure and a homogeneous size distribution near to 150 nm, with a high intensity and colorimetric data, reducing drastically the temperature and energy consumption to obtain a black ceramic pigment suitable to be utilized in digital ceramic inks. Full article

Amines with two carbon atoms in the organic chain [ethylamine (EA), diethylamine (DEA), triethylamine (TEA)] have been used as precipitant agents to obtain a hydrotalcite-like compound with Zn (II) and Al (III) as layered cations and with nitrate anions in the interlayered region to balance the charge. This Layered Double Hydroxide was prepared following the coprecipitation method, and the effect on the crystal and particle sizes was studied. Also, the effect of submitting the obtained solids to hydrothermal post-synthesis treatment by conventional heating and microwave assisted heating were studied. The obtained solids were exhaustively characterized using several instrumental techniques, such as X-ray diffraction, Thermal Analysis (DTA and TG), Chemical Analysis, Infrared Spectroscopy (FT-IR), determination of Particle Size Distribution and BET-Surface area. Well crystallized solids were obtained showing two possible LDH phases, depending on the orientation of the interlayer anion with respect to the brucite-like layers. The results indicated that there is a certain influence of the amine, when used as a precipitating agent, and as a consequence of the degree of substitution, on the crystallinity and particle size of the final solid obtained. The LDHs obtained using TEA exhibited higher crystallinity, which was improved after a long hydrothermal treatment by conventional heating. Regarding the shape of the particles, the formation of aggregates in the former solid was detected, which could be easily disintegrated using ultrasound treatments, producing solid powder with high crystallinity and small particle size, with homogeneous size distribution. Full article

The developing significance of adsorption has brought about a steadily expanding quantity of logical and innovative writing on different adsorbents. This paper intends to propose experimental and computational methods for measuring the strength of adsorbate–solid interactions. It primarily focuses on the use of graphs to measure the effectiveness of an adsorbate’s bonds with the solid adsorbent by determining the isosteric heat. The Clausius–Clapeyron model equation is used to determine the isosteric enthalpy of adsorption from two adsorption isotherms at various but close temperatures, with ΔT of 10 °C. A full computational explanation of the Clausius–Clapeyron model equation for determining ΔH_ads is provided using experimental data. Logarithmic plots of uptakes vs. p in the low-pressure zone for the Freundlich–Langmuir graph are used to assess and confirm the quality of the crucial underlying isotherms. The isosteric heat was found to be between 13.5 kJ/mol and 16 kJ/mol. Full article

Currently, the use of alternative solvents is increasing, namely ionic liquids (ILs) and deep eutectic solvents (DESs) in diverse fields of knowledge, such as biochemistry, chemistry, chemical engineering, biotechnology and biomedicine. Particularly, when compared to traditional solvents, these alternative solvents have great importance for biomolecules due to the enhanced solubility, structure stability and the biological activity of biomolecules, such as protein and enzymes. Thus, in this review article, the recent developments and efforts on the technological developments carried out with ILs and DESs for the stabilization and activation of proteins and enzymes are provided. The most studied IL- and DES-based formulations for proteins and enzymes are discussed and the molecular mechanisms and interactions related to the increased stability promoted by these alternative solvents are disclosed, while emphasizing their main advantages. Full article

In recent decades, the environmental impact caused by greenhouse gases, especially CO₂, has driven many countries to reduce the concentration of these gases. The study and development of new designs that maximise the efficiency of CO₂ capture continue to be topical. This paper presents a review of the application of hydrotalcites as CO₂ sinks. There are several parameters that can make hydrotalcites suitable for use as CO₂ sinks. The first question is the use of calcined or uncalcined hydrotalcite as well as the temperature at which it is calcined, since the calcination conditions (temperature, rate and duration) are important parameters determining structure recovery. Other aspects were also analysed: (i) the influence of the pH of the synthesis; (ii) the molar ratio of its main elements; (iii) ways to increase the specific area of hydrotalcites; (iv) pressure, temperature, humidity and time in CO₂ absorption; and (v) combined use of hydrotalcites and cement-based materials. A summary of the results obtained so far in terms of CO₂ capture with the parameters described above is presented. This work can be used as a guide to address CO₂ capture with hydrotalcites by showing where the information gaps are and where researchers should apply their efforts. Full article

In this work, we investigate the potential of a novel carbon composite as an electrode for high-voltage electrochemical double-layer capacitors. The carbon composite was prepared following a sustainable synthetic approach that first involved the pyrolysis and then the activation of a precursor formed by winery wastes and graphene oxide. The composite prepared in this way shows a very high specific surface area (2467 m²·g⁻¹) and an optimum pore size distribution for their use in supercapacitor electrodes. Graphene-biowaste-derived carbon composites are tested as active electrode materials in two different non-aqueous electrolytes, the ammonium salt-based conventional organic electrolyte and one imidazolium-based ionic liquid (1 M Et₄NBF₄/ACN and EMINTFSI). It was found that the presence of graphene oxide led to significant morphological and textural changes, which result in high-energy and power densities of ~27 W·h·kg⁻¹ at 13,026 W·kg⁻¹. Moreover, the devices assembled retain above 70% of the initial capacitance after 6000 cycles in the case of the organic electrolyte. Full article

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 (NO_x) 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