ChemEngineering — Open Access Journal

For the preparation and characterization of several layer double hydroxides (LDH) with inorganic interlayer anions (carbonate and nitrate) and nanohybrids, two organo-LDHs were studied in detail. The dodecylbenzene sulfonate (DBS) was used as an organic interlayer anion to modify the hydrophilic nature of the interlayer. The aim of the modification of the layered double hydroxides (LDH) was to change the hydrophilic character of the interlayer to hydrophobic with the purpose of improving its ability to adsorb several (anionic and cationic) dyes from water. These compounds have been used as adsorbents of amaranth (Am), diamine green B (DGB) and brilliant green (BG) dyes. Adsorption tests were conducted using variable pH values, contact times and initial dye concentrations (adsorption isotherms) to identify the optimum conditions for the intended purpose. Adsorbents and adsorption products were characterized by several physicochemical techniques. The results of the adsorption tests showed that the organo-LDH nanohybrids could be efficient adsorbents in the removal of studied dyes from water. Thus, it can be concluded that nanohybrids studied in this work might act as suitable supports in the design of adsorbents for the removal of a wide spectrum of dyes with the aim of reducing the adverse effects on water resources. Full article

Phosphorus as phosphate and nitrogen as ammonium or nitrate are the main nutrients in wastewaters and agricultural sludges. They runoff easily to waterways and cause eutrophication in water bodies. However, ammonium and phosphate could be precipitated simultaneously and used as recycled nutrients. In this research, dolomite calcined at 650 °C, 750 °C, or 950 °C and commercial MgO were used as precipitants in simultaneous phosphate and ammonium removal from synthetic (NH₄)₂HPO₄ solution and agricultural sludge. Calcination at 750 °C was the preferred option as dolomite was decomposed to MgO and CaCO₃ for optimal struvite precipitation. Molar ratios of 1.1–1.6:1–2:2 (Mg:P:N) were employed in the experiments. Very robust ammonium removal was obtained with MgO (57%), dolomite 650 °C and dolomite 750 °C (75%). MgO removed almost all phosphate, while dolomite 650 °C removed 65%, and dolomite 750 °C removed 60% (70% from agricultural sludge). Some part of the phosphate was adsorbed, most likely by CaCO₃, during dolomite precipitation. Struvite was the only identified reaction product in all samples after 24 h of precipitation. Calcined dolomite had great potential in ammonium and phosphate precipitation from both synthetic waters and agricultural sludges and the precipitates could be used as recycled fertilizers. Full article

In order to minimize unintentional discharge, supercapacitors are interfaced with a membrane that separates the anode from the cathode—this membrane is called the separator. We focus here on separators, which are structured as electronic diode-like. We call an electrically structured separator “the gate”. Through experiments, it was demonstrated that ionic liquid-filled supercapacitors, which were interfaced with gated separators exhibited a substantial capacitance (C) increase and reduction in the equivalent series resistance (ESR) compared to cells with ordinary separators. These two attributes help to increase the energy, which is stored in a cell, since for a given cell’s voltage, the dissipated energy on the cell, U_R = V²/4(ESR) and the stored energy, U_C = CV²/2, would increase. These were indeed ionic diodes since the order of the diode layout mattered—the diode-like structures exhibited maximum capacitance when their p-side faced the auxiliary electrode. Full article

This study investigates the synthesis of [Ni_0.80Co_0.15]_(1−x)/0.95Al_x(OH)₂ (x = 0–0.2) materials by coprecipitation to understand the formation of layered double hydroxide (LDH) phases as influenced by Al content and synthesis route. Two routes were compared: the first method dissolved all the metal reagents into one solution before addition into the reaction vessel, while the second dissolved Al into a separate NaOH solution before simultaneous addition of the Ni/Co and Al solutions into the reaction vessel. The synthesized materials were characterized by Scanning Electron Microscopy, X-ray Diffraction, Inductively Coupled Plasma-Optical Emissions Spectroscopy and Thermogravimetric Analysis to understand the formation of LDH phases as influenced by Al content and synthesis method. It was found that as Al content increased, the amount of LDH phase present increased as well. No significant difference in LDH phase presence was observed for the two synthesis methods, but the morphologies of the particles were different. The method containing all the metals in one solution produced small particles, likely due to the continuous nucleation of Al(OH)₃ disrupting particle growth. The method containing the separate Al in NaOH solution matched the morphology of the material with no Al, which is known to form desired large spherical particles under continuously stirring tank reactor synthesis conditions. Full article

We present a high-scale method to produce few-layer graphene (FLG) based on the mechanical exfoliation of graphite and compare the obtained FLG with the one reported earlier arising from pencil lead ablation. Several elements were modified and improved in the new approach. The purification and the ablation set-up were simplified, and the morphology of the FLG was modified and improved in view of some applications. The morphology-dependent properties of FLGs, lead-FLG, and graphite-FLG as conductive layers and in nanocomposites were investigated. The newly obtained FLG had a higher aspect ratio (high lateral size vs thickness/higher 2D aspect), which is reflected by enhanced transparency–conductivity features of the layer (film) and elongation-at-break behavior of the polymer composites. On the contrary, the nanocomposite containing lead-FLG showed, for instance, excellent gas barrier properties due to the multi-step structure of the lead-FLG flakes. Such structure exhibited less 2D and more 3D character, which can be highly suitable for applications where the presence of active/reactive edges is beneficial, e.g., in catalysis or supercapacitors’ electrodes. Nuclear reaction analysis was employed to investigate the morphology of graphite-FLG film. Full article

From the point of view of finite time thermodynamics, the performance boundaries of thermal machines are considered, taking into account the irreversibility of the heat exchange processes of the working fluid with hot and cold sources. We show how the dynamics of heat exchange affects the shape of the optimal cycle of a heat engine and its performance, in particular, energy conversion efficiency in the maximum power mode. This energy conversion efficiency can depend only on the ratio of the heat transfer coefficients to the sources, or not depend on them at all. A class of dynamic functions corresponding to “natural” requirements is introduced and it is shown that, for any dynamics from this class, the optimal cycle consists of two isotherms and two adiabats, not only for the maximum power problem, but also for the problem of maximum energy conversion efficiency at a given power. Examples are given for calculating the parameters of the optimal cycle for the cases when the heat transfer coefficient to the cold source is arbitrarily large, and for dynamics in the form of a linear phenomenological (Fourier heat transfer) law. Full article

This work highlights how the treatment of ZSM-5 (parent Zeolite Socony Mobil–5, Si/Al = 23) with different surfactant templates and alkaline solution, improved the catalytic performance in the Friedel-Crafts acylation of anisole with a propionic anhydride to obtain p-methoxypropiophenone. The modified microporous to mesoporous zeolite catalysts were characterized using different analytical techniques, including X-ray diffraction (XRD), nitrogen porosimetry, Fourier-transform infrared spectroscopy (FT-IR), temperature-programmed desorption (ammonia-TPD) and field emission scanning electron microscopy (FE-SEM) to analyze the crystallographic structure, surface acidity, surface area, porosity, morphology, and particle size. The results showed that the formed mesoporous zeolite by NaOH solution had smaller mesopores (ca. 3.7 nm) as compared to the mesoporous zeolites obtained by surfactant templates, such as, CTAB (ca. 14.9 nm), TPAOH (ca. 11.1 nm) and mixture of CTAB/TPAOH (ca. 15.2 nm). The catalytic acylation reaction was conducted in a batch glass reactor at various temperatures and the products were analyzed using off-line gas chromatography–mass spectrometry (GC-MS). It was found that the activity of treated ZSM-5 with mixed surfactant templates (CTAB/TPAOH) exhibited enhanced selectivity towards the main product (p-methoxypropiophenone) by a factor 1.7 or higher than unmodified ZSM-5 due to its increased surface area by 1.5 times and enhanced acid sites. Full article

This contribution elaborates the design considerations of a simplified version of a four-product multiple dividing wall column in pilot plant scale that will be built at Ulm University. This will be the first realization of a multiple dividing wall column worldwide. A detailed simulation approach, starting from the initialization by V_min-method, is presented to obtain a feasible design of the column, taking into account the constraints of the operation within a university environment. The operating point was found by simulation studies, using the integrated optimization tool of AspenPlus^© V10. It is shown that an NQ-curve can be applied on simplified multiple dividing wall columns. Based on the determined operating point, the thermodynamic and the fluid dynamic design of the pilot plant are discussed in detail. It is shown that the designed column can be operated to obtain all products with a purity of at least 98 mol%. Full article

Nanosized titanium dioxide (TiO₂) nanoparticles were used for the photocatalytic reduction of hexavalent chromium in the presence of formic acid. The photoreduction of Cr(VI) in the absence of formic acid was quite slow. When formic acid was added in the chromium solution as the hole scavenger, a rapid photocatalytic reduction of Cr(VI) was observed, owing to the consumption of hole and the acceleration of the oxidation reaction. Furthermore, three commercial TiO₂ nanoparticles (AEROXIDE^® P25; Ishihara Sangyo ST-01; FUJIFILM Wako Pure Chemical Corp.) were evaluated for the photoactivity of reduction of Cr(VI). Full article

Levulinic acid (LA) has been ranked as one of the “Top 10” building blocks for future bio-refineries as proposed by the US Department of Energy. It is considered one of the most important platform molecules for the production of fine chemicals and fuels based on its compatibility with existing processes, market economics, and industrial ability to serve as a platform for the synthesis of important derivatives. Hydrogenation of LA to produce γ-valerolactone (GVL) is an active area of research due to the potential of GVL to be used as a biofuel in its own right and for its subsequent transformation into hydrocarbon fuels. This paper contains a new design for a simple, cost effective, and safe hydrogenation reactor for the transformation of levulinic acid to γ-valerolactone (GVL) by utilizing high boiling point organic fluid. The hydrogenation reactor is composed of a heating source—organic fluid (called “DOWTHERM A” or “thermex”) and the catalytic reactor. The advantages of high boiling temperature fluids, along with advances in hydrocracking and reforming technologies driven by the oil and gas industries, make the organic concept more suitable and safer (water coming in contact with liquid metal is well understood in the metallurgical industry to be a steam explosion hazard) for heating the hydrogenation reactor. COMSOL multi-physics software version 4.3b was applied in this work and simultaneously solves the continuity, Navier-Stokes (fluid flow), energy (heat transfer), and diffusion with chemical reaction kinetics equations. It was shown that the heat flux supplied by the DOWTHERM A organic fluid could provide the necessary heat flux required for maintaining the hydrogenation process. It was found that the mass fractions of hydrogen and levulinic acid decreased along the reactor axis. The GVL mass fraction increased along the reactor axis. Full article

Water is a key resource for sustainable development and plays a crucial role in human development. Desalination is one of the most promising technologies to mitigate the emerging water crisis. Thermal desalination and reverse osmosis are two of the most widely employed desalination technologies in the world. However, these technologies are energy intensive. Clathrate-hydrate-based desalination (HyDesal) is a potential energy-efficient desalination technology to strengthen the energy–water nexus. In our previous study, we proposed a ColdEn-HyDesal process utilizing waste Liquefied Natural Gas (LNG) cold energy based on a fixed-bed reactor configuration. In this study, we evaluated the effect of 10% propane in three different gas mixtures, namely, nitrogen (G1), argon (G2), and carbon dioxide (G3), as hydrate formers for the HyDesal process. The achieved water recovery was very low (~2%) in the presence of NaCl in the solution for gas mixtures G1 and G2. However, high water recovery and faster kinetics were achieved with the G3 mixture. To improve the water recovery and kinetics of hydrate formation for the G2 gas mixture, the effect of sodium dodecyl sulfate (SDS) was evaluated. The addition of SDS did improve the kinetics and water recovery significantly. Full article

Several hydrotalcite-type compounds with different divalent (Mg²⁺, Ni²⁺, Cu²⁺, Zn²⁺) and trivalent (Al³⁺, Cr³⁺) cations and different ratio compositions were tested for the isomerization of linoleic acid in order to study their role on the obtention of specific conjugated linoleic acids (CLAs) with anticarcinogenic and nutritional properties. This is a complex reaction due to the high number of possible isomers of linoleic acid together with the significant competition of the isomerization reaction with other secondary undesired reactions. All catalysts showed very high conversions of linoleic acid, but condensation products were mainly obtained, especially for the hydrotalcite-type compounds with higher Mg/Al ratios due to their higher Brønsted basicity and for the catalysts with higher Ni²⁺ content or with the presence of Cu²⁺, Zn²⁺ in the layers because of the influence of the higher acidity of these cations on the Brønsted basicity of the hydroxides. The best results were achieved for the catalysts with Mg/Al ratio around 2.5–3, resulting in 29–38% of selectivity to the identified CLAs. Full article

Layered double hydroxides (LDH) or their derived mixed oxides present marked acid-base properties useful in catalysis, but they are generally agglomerated, inducing weak accessibility to the active sites. In the search for improving dispersion and accessibility of the active sites and for controlling the hydrophilic/hydrophobic balance in the catalysts, nanocomposite materials appear among the most attractive. In this study, a series of nanocomposites composed of LDH and reduced graphene oxide (rGO), were successfully obtained by direct coprecipitation and investigated as base catalysts for the Claisen–Schmidt condensation reaction between acetophenone and benzaldehyde. After activation, the LDH-rGO nanocomposites exhibited improved catalytic properties compared to bare LDH. Moreover, they reveal great versatility to tune the selectivity through their composition and the nature or the absence of solvent. This is due to the enhanced basicity of the nanocomposites as the LDH content increases which is assigned to the higher dispersion of the nanoplatelets in comparison to bulk LDH. Lewis-type basic sites of higher strength and accessibility are thus created. The nature of the solvent mainly acts through its acidity able to poison the basic sites of the nanocatalysts. Full article

Micro-environments in black shale are reactors for geochemical reactions that differ from the bulk scale. They occur in small isolated pores of several 10 s to 100 s of nanometers without or with limited ionic exchange by diffusion to the surrounding matrix. The example of the formation of titania polymorphs brookite (and anatase) in black shale demonstrates that pH < 4 of the pore waters or lower must prevail to enable dissolution of Ti-bearing precursors followed by the precipitation of these metastable solids. Comparably low pH is applied during the industrial production of nanometer-sized brookite or anatase by sol-gel methods. The process parameters during industrial production such as low pH, negative Eh, or low ionic strength (to promote agglomeration) allow a comparison with parameters during geochemical processes leading to titania formation in black shale. Sol-gel processes are suggested herein as key geochemical processes in micro-environments of black shale in order to understand the formation of single brookite crystals or agglomerates on a nanometer scale. Full article

The packing material selection for a bioreactor is an important factor to consider, since the characteristics of this material can directly affect the performance of the bioprocess, as well as the investment costs. Different types of low cost packing materials were studied in columns to reduce the initial and operational costs of biogas biodesulfurization. The most prominent (PVC pieces from construction pipes) was applied in a bench-scale biotrickling filter to remove the H₂S of the biogas from a real sewage treatment plant in Brazil, responsible for 90 thousand inhabitants. At the optimal experimental condition, the reactor presented a Removal Efficiency (RE) of up to 95.72% and Elimination Capacity (EC) of 98 gS·m⁻³·h⁻¹, similar to open pore polyurethane foam, the traditional material widely used for H₂S removal. These results demonstrated the high potential of application of this packing material in a full scale considering the robustness of the system filled with this support, even when submitted to high sulfide concentration, fluctuations in H₂S content in biogas, and temperature variations. Full article

This work presents a new insight into the potential of a Ni/CeZrO₂ catalyst in two separate processes: (i) Chemical Vapor Deposition (CVD) using methane as a feedstock to obtain carbon nanotubes (CNTs) and H₂, and (ii) catalyst regeneration with H₂O that yields H₂. The direct reaction of methane with H₂O (steam methane reforming (SMR)) leads to H₂ and CO (and CO₂), whereas carbon deposition—regardless of its type—is an unwanted reaction. The concept presented in this work assumes dividing that process into two reactors, which allows one to obtain two valuable products, i.e., CNTs and H₂. The literature data on CNT production via CVD ignores the issue of H₂ formation. Moreover, there is no data concerning CNT production in fluidized bed reactors over ceria-zirconia supported metal catalysts. The results presented in this work show that CNTs can be formed on Ni/CeZrO₂ during CH₄ decomposition, and that the catalyst can be easily regenerated with H₂O, which is accompanied by a high production of H₂. The ability of Ni/CeZrO2 to be regenerated is its main advantage over the Ni-MgO catalyst that is popular for CNT production. This paper also shows that the Ni/CeZrO₂ catalyst has the potential to be used for CNT and H₂ production in a larger scale process, e.g., in a fluidized bed reactor. Full article

In this work, a ceria-zirconia supported nickel catalyst (Ni/CeZrO₂) was for the first time used in a fluidized bed reactor in order to obtain carbon nanotubes (CNTs) and H₂ in the reaction of the decomposition of CH₄. The same catalyst was afterward regenerated with H₂O, which was accompanied with the production of H₂. The impact of catalyst granulation, temperature, and gas hourly space velocity (GHSV) on the amount and type of carbon deposits was determined using thermogravimetric analysis (TGA) and scanning and transmission electron microscopy (SEM and TEM). The presence of randomly oriented and curved CNTs with an outer diameter of up to 64 nm was proved. The Ni/CeZrO₂ particles were loosely covered with CNTs, freely dispersed over CNTs, and strongly attached to the external CNT walls. TEM proved the presence of a Ni/CeZrO₂@CNT hybrid material that can be further used as catalyst, e.g., in WGS or DRM reactions. The impact of GHSV on hydrogen production during catalyst regeneration was determined. The catalyst was subjected to cyclic tests of CH₄ decomposition and regeneration. According to the obtained results, Ni/CeZrO₂ can be used in CH₄ conversion to CNTs and H₂ (instead of CH₄ combustion), e.g., in the vicinity of installations that require methane utilization. Full article

Carbon materials play a crucial role in sorbents and heterogeneous catalysis and are widely used as catalyst support for several reactions. This paper reports on an investigation of tungsten carbide (W₂C) catalyst on three types of carbon support, namely activated carbon (AC), carbon nanofibers (CNF) and carbon-covered alumina (CCA). We evaluated their activity and selectivity in stearic acid hydrodeoxygenation at 350 °C and 30 bar H₂. Although all three W₂C catalysts displayed similar intrinsic catalytic activities, the support did influence product distribution. At low conversions (<5%), W₂C/AC yielded the highest amount of oxygenates relative to W₂C/CNF and W₂C/CCA. This suggests that the conversion of oxygenates into hydrocarbons is more difficult over W₂C/AC than over W₂C/CNF and W₂C/CCA, which we relate to the lower acidity and smaller pore size of W₂C/AC. The support also had an influence on the C18-unsaturated/C18-saturated ratio. At conversions below 30%, W₂C/CNF presented the highest C18-unsaturated/C18-saturated ratio in product distribution, which we attribute to the higher mesopore volume of CNF. However, at higher conversions (>50%), W₂C/CCA presented the highest C18-unsaturated/C18-saturated ratio in product distribution, which appears to be linked to W₂C/CCA having the highest ratio of acid/metallic sites. Full article

Modeling is a powerful tool for the design and development of proton exchange membrane fuel cells (PEMFCs). This study presents a one-dimensional, two-phase mathematical model of PEMFC to investigate the two-phase transport process, gas species transport flow and water crossover fluxes. The model reduces the computational time for PEMFC design with guaranteed accuracy. Analysis results show that the concentration and activation overpotentials of the cell decrease with the increase of operation pressure, which result in enhanced cell performance. Proper oxygen stoichiometry ratio in the cathode decreases the cell activation overpotential and is favorable for performance improvement. The cell ohmic resistance correspondingly increases with the increase of catalyst layer thickness, which leads to a deteriorated cell performance. The improvement on cell performance could be facilitated by decreasing the membrane thickness. Predicted results show that the present model is a useful tool for the design optimization of practical PEMFCs. Full article