ChemEngineering — Open Access Journal

The goal of this work is to assess the application of ultrasonic power to the reactive dissolution of limestone particles in an acidic environment; this would represent a novel method for improving wet Flue Gas Desulfurization industrial systems. In this study a stepwise titration method is utilized; experiments were done by using different particle size distributions with and without the application of ultrasound. The use of ultrasonic power sensibly affected the reaction rate of limestone and its dissolution; a major difference could be observed when samples from the Wolica region in Poland were studied. In this case, the overall dissolution rate was found to increase by more than 70%. The reactive dissolution of limestone does not follow the same mathematical model when sonication is in effect; in this case, an extra Ultrasonic Enhancement Constant was introduced. It was demonstrated that the dissolution is proportional to an Effective Reaction Surface and, therefore, surface interactions should also be taken into consideration. For this purpose, a study is presented here on the Z-potential and electrophoretic mobility of limestone samples measured in aqueous dispersions by means of Laser Doppler Micro-Electrophoresis. Full article

Coating open-cell foams by a catalytic layer is a necessary step to obtain structured catalytic foam reactors. The dip-coating method, consisting of immersing the foam in a suspension or in a sol-gel, is generally used to obtain the coating. The excess of liquid has to be evacuated from the foam to obtain a thin layer. Different methods to remove this excess of liquid have been investigated in the present work. The objective was to show that 3D X-ray tomography coupled to image analysis could be a tool to discriminate the methods by analysing the spatial localisation of the catalyst layer throughout the whole foam samples. A simple blowing by air in every direction seems to not be appropriate to obtain uniform coatings. Full article

A volume-of-fluid (VOF) finite volume model under the ANSYS^® Fluent framework was coupled with the response surface method (RSM) to find the best operating conditions within a jettability window for two selected responses in a drop-on-demand inkjet printing process. Twenty-five runs were generated using a face centred design and numerical simulations were carried out using viscosity, surface tension, nozzle diameter, and inlet velocity as input factors. A mesh study was first conducted to establish the necessary number of cells to best combine accuracy and expended time. Selected runs were discussed, identifying the underpinning mechanisms behind the droplet generation at different time periods. Each one of the responses was evaluated under different input factors and their effects were identified. Finally, the desirability function concept was advantageously used to proceed with a multiple optimization where all the responses were targeted under usual jettability/printability conditions. Full article

In this study, a directly irradiated, milli-scale chemical reactor with a simple nickel catalyst was designed for dry reforming of methane for syngas. A milli-scale reactor was used to facilitate rapid heating, which is conducive to combating thermal transience caused by intermittent solar energy, as well as reducing startup times. Milli-scale reactors also allow for a distributed and modular process to produce chemicals on a more local scale. In this setup, the catalyst involved in the reaction is located directly in the focal area of the solar simulator, resulting in rapid heating. The effects of mean residence time and temperature on conversion and energy efficiency were tested. The process, which is intended to store thermal energy as chemical enthalpy, achieved 10% thermal-to-chemical energy conversion efficiency at a mean residence time of 0.028 s, temperature of 1000 °C, and molar feed ratio of 1:1 CO₂:CH₄. A significant portion of the thermal energy input into the reactor was directed toward sensible heating of the feed gas. Thus, this technology has potential to achieve solar-to-chemical efficiency with the integration of recuperative heat exchange. Full article

CMK-3 mesoporous carbon was nanocast from SBA-15 silica. The obtained carbon was characterized by nitrogen sorption isotherms, X-ray diffraction and transmission electron microscopy (TEM). The batch adsorption tests were done at constant pH taking into account the initial metal ion concentration, adsorbent mass and temperature. A statistical study using a response surface design method was done to develop a mathematical model to predict copper adsorption on CMK-3 as a function of the mentioned experimental factors. It was found that all these parameters are significant, and copper concentration has the greatest effect on adsorption among them. Moreover, the obtained model proved to be adequate in predicting copper adsorption on CMK-3 and its performance under different experimental conditions. Full article

The present work is a study of CO₂ Reforming of Methane (DRM) carried out in a catalytic Pd-based membrane reactor. A detailed thermodynamic analysis is carried out, calculating the chemical equilibrium parameters in two different cases: (a) DRM along with the Reverse Water Gas Shift (RWGS) reaction and (b) DRM along with both RWGS and the Boudouard Reaction (BR). The performance of membrane reactor is then experimentally analyzed in terms of methane conversion, hydrogen recovery and H₂/CO reaction selectivity by varying feed pressure and CO₂/CH₄ feed molar ratio and 500 °C and GHSV = 100 h⁻¹. Among the obtained results, a CH₄ conversion of about 26% and a H₂ recovery of 47% are achieved at low feed pressures, exceeding the traditional reactor equilibrium conversion. This effect can be attributed to the favorable thermodynamics coupled to the hydrogen permeation through the membrane. This study further demonstrates the general effectiveness of membrane-integrated reaction processes, which makes the production of syngas more efficient and performing, providing important environmental benefits. Full article

In an aqueous enzymatic saccharification using cellulase, the dissolution of crystalline cellulose is one of the rate-limiting steps. Insoluble cellulose powder was preliminarily heat-treated with ionic liquids (ILs), such as [Bmim][Cl] (1-butyl-3-methylimidazolium chloride) and [Amim][Cl] (1-allyl-3-methylimidazolium chloride), which enable the production of soluble cellulose. On the other hand, the presence of ILs leads to a denaturation of enzymes. Using cellulase from Trichoderma viride, the effects of [Bmim][Cl] and [Amim][Cl] in the enzymatic saccharification were compared. The production of glucose was optimized with 5 wt%-ILs, both for [Bmim][Cl] and for [Amim][Cl]. The significant inhibiting effects of ILs (IL concentration >10 wt%) could be due to the denaturation of cellulase, because the peak shifts of intrinsic tryptophan fluorescence were observed in the presence of 7.5 wt%-ILs. To analyze kinetic parameters, the Langmuir adsorption model and the Michaelis-Menten model were employed. The investigation suggests that [Amim][Cl] can provide soluble cellulose more efficiently, and can promote enzymatic saccharification in the IL concentration below 5 wt%. Full article

This study aimed at investigating the effect of l-ascorbic acid on the Cu²⁺-induced oxidation of quercetin, within a pH range from 6.7 to 8.3 and temperatures varying from 53 to 87 °C. Initial examinations showed that quercetin degradation obeyed apparent first-order kinetics and it was significantly affected by temperature. Modelling of the effect of l-ascorbic acid by implementing response surface methodology suggested that l-ascorbic acid did not impact quercetin oxidation significantly (p < 0.05) and led to an empirical kinetic model based on temperature (T) and pH. Liquid chromatography–diode array–mass spectrometry analyses revealed the presence of typical quercetin degradation and oxidation products, including protocatechuic acid and 2-(hydroxybenzoyl)-2-hydroxybenzofuran-3(2H)-one. It was concluded that the formation of l-ascorbyl or other radicals (superoxide anion) may be involved in quercetin oxidation and this fact merits further attention to illuminate the possible beneficial or adverse nutritional consequences of such reactions in foods. Full article

Lignocellulosic agricultural side products like wheat straw are widely seen as an important contribution to a sustainable future economy. However, the optimization of biorefinery processes, especially the pretreatment step, is crucial for an economically viable biorefinery. The monitoring of this pretreatment process in terms of delignification and the generation of the fermentation inhibitors acetic acid, furfural, and hydroxymethylfurfural (HMF) is essential in order to adapt the process parameters for a desired outcome and an economical operation. However, traditional wet chemistry methods are time-consuming and not suitable for on-line process monitoring. Therefore, UV-Vis spectroscopy in combination with partial least-squares regression was used for the determination of the concentrations of lignin, acetic acid, furfural, and HMF. Five different data blocks with increasing amounts of impurities were investigated to evaluate the influence of the inevitable impurities on the calibration models. Lignin showed a good prediction accuracy with 95% tolerance intervals between ±0.46 to ±1.6 mg/L for concentrations up to 30 mg/L. Also, the other components could be predicted with a sufficient accuracy for on-line process monitoring. A satisfactory calibration can be obtained with 10 to 20 reference samples valid at process temperatures between 160 °C and 180 °C. Full article

The ferrite body is the origin of crack and corrosion initiation of steels. Distribution and density of ferrite in seven steel ingots were examined by light optical microscopy and computational modeling, in the study, to explore the correlation of ferrite formation to chemical composition and the mushy zone temperature in ingot forming. The central segregation phenomenon in ferrite distribution was observed in all the examined steel specimens, except 0Cr17Ni4Cu4Nb stainless steel. No significant difference was found in the distribution and density of ferrite among zones of the surface, ½ radius, and core in neither the risers nor tails of 0Cr17Ni4Cu4Nb ingots. Additionally, fewer ferrites were found in 0Cr17Ni4Cu4Nb compared to other examined steels. The difference of ferrite formation in 0Cr17Ni4Cu4Nb elicited a debate on the traditional models explicating ferrite formation. Considering the compelling advantages in mechanical strength, plasticity, and corrosion resistance, further investigation on the unusual ferrite formation in 0Cr17Ni4Cu4Nb would help understand the mechanism to improve steel quality. In summary, we observed that ferrite formation in steel was correlated with the mushy zone temperature. The advantages of 0Crl7Ni4Cu4Nb in corrosion resistance and mechanical stability could be the result of fewer ferrites being formed and distributed in a scattered manner in the microstructure of the steel. Full article

The Danish government has set an ambitious target to achieve 100% fossil independence across all energy sectors, which demands optimum utilization of renewable energy sources, such as wind and biogas, by 2050. Biogas production has increased, and the upgrading of biogas offers a broad range of applications, such as transportation, and gas grid injection for downstream utilization. The biogas has to meet natural gas quality prior to injection into the gas grid system. The investment costs of the gas grid, upgrading cost, and gas compression costs are the major challenges for integrating the biogas into the existing gas infrastructure. In this investigation, the Wobbe index (WI) for raw biogas and upgraded biogas was measured to evaluate the scenario for biogas injection into the gas grid system. It was found that raw biogas has to improve its WI from 28.3 MJ/m³(n) to a minimum of 50.76 MJ/m³(n) via upgrading, and compressed to 40 bar system, to supply the gas grid system for trading. Then, yearly gas consumption by larger gas consumers was studied to evaluate the alternative approach of biogas utilization to save upgrading and compression costs for gas grid injection. Full article

The development of sustainable yet efficient technologies to store solar light into high energy molecules, such as hydrocarbons and hydrogen, is a pivotal challenge in 21st century society. In the field of photocatalysis, a wide variety of chemical routes can be pursued to obtain solar fuels but the two most promising are carbon dioxide photoreduction and photoreforming of biomass-derived substrates. Despite their great potentialities, these technologies still need to be improved to represent a reliable alternative to traditional fuels, in terms of both catalyst design and photoreactor engineering. This review highlights the chemical fundamentals of different photocatalytic reactions for solar fuels production and provides a mechanistic insight on proposed reaction pathways. Also, possible cutting-edge strategies to obtain solar fuels are reported, focusing on how the chemical bases of the investigated reaction affect experimental choices. Full article

The paper describes results from operating a new 3-step membrane-based process targeted at separating Mg²⁺ from seawater in an inexpensive way, with the purpose of using it to enrich desalinated water with magnesium, with as little as possible Cl⁻ and Na⁺ addition. To this end, seawater undergoes a series of processes aimed at increasing the Mg²⁺ concentration from ~1350 to ~4000 mg/L through nanofiltration while the monovalent ion concentrations are reduced by a nanofiltration-diananofiltration sequence, in which the diluent is RO produced water from a desalination plant. A dense ultrafiltration (UF) step precedes the nanofiltration-diananofiltration (NF-DiaNF) cycles. In this step sulfate in seawater is rejected better than divalent cations hence the retentate of this step has a ratio of total hardness to sulfate (([Ca²⁺] + [Mg²⁺])/[SO₄²⁻] → 1) which enables attaining an almost complete washout of monovalent ions in the DiaNF step. The paper is concluded with presentation of general design of the process steps and a cost assessment, which shows the process to be both flexible in the quality of the rich Mg solution generated, and cost competitive, relative to other alternatives. Full article

Nanocrystalline copper oxide thin films were fabricated by reactive DC magnetron sputtering. The structure and optical properties of the films were measured with X-ray diffraction, scanning electron microscopy, and spectrophotometry. Variations of oxygen partial pressure resulted in oxide composition ranging from Cu, Cu-Cu₂O, Cu₂O-CuO_1−x, and CuO. Optical band transitions at 2.06 eV and 2.55 eV were found for Cu₂O corresponding to the direct forbidden and direct allowed interband transitions. For CuO an indirect allowed interband transition was found at 1.28 eV. The photocatalytic activity was determined by quantifying the rate constant and quantum yield (destroyed molecules/photons absorbed) under stearic acid degradation. Photocatalytic activity was found to be highest in mixed-phase films with Cu-Cu₂O films the highest. Results from post-annealed Cu-Cu₂O and CuO films show similar results. We interpret our results as being due to efficient electron-hole charge separation in the heterojunction films. The obtained quantum yields were generally about ten times lower than for comparable dense TiO₂ and WO₃ binary oxides, which calls for further studies of the spectral dependence of the quantum yield and electron-hole pair life times for oxides with different purity levels. Full article

Phase transition, and more specifically bubble formation, plays an important role in many industrial applications, where bubbles are formed as a consequence of reaction such as in electrolytic processes or fermentation. Predictive tools, such as numerical models, are thus required to study, design or optimize these processes. This paper aims at providing a meso-scale modelling description of gas–liquid bubbly flows including heterogeneous bubble nucleation using a Discrete Bubble Model (DBM), which tracks each bubble individually and which has been extended to include phase transition. The model is able to initialize gas pockets (as spherical bubbles) representing randomly generated conical nucleation sites, which can host, grow and detach a bubble. To demonstrate its capabilities, the model was used to study the formation of bubbles on a surface as a result of supersaturation. A higher supersaturation results in a faster rate of nucleation, which means more bubbles in the column. A clear depletion effect could be observed during the initial growth of the bubbles, due to insufficient mixing. Full article

With the increasing utilization of fossil fuels in today’s technological world, the atmosphere’s concentration of greenhouse gases is increasing and needs to be controlled. In order to achieve this goal, it is imperative to have sensors that can provide data on the greenhouse gases in the environment. The recent literature contains a few publications that detail the use of new methods and materials for sensing these gases. The first part of this review is focused on the possible effects of greenhouse gases in the atmosphere, and the second part surveys the developments of sensors for greenhouse gases with coverage on carbon nano-materials and composites directed towards sensing gases like CO₂, CH₄, and NO_x. With carbon dioxide measurements, due consideration is given to the dissolved carbon dioxide gas in water (moisture). The density functional calculations project that Pd-doped single-walled carbon nanotubes are ideal for the development of NO_x sensors. The current trend is to make sensors using 3D printing or inkjet printing in order to allow for the achievement of ppb levels of sensitivity that have not been realized before. This review is to elaborate on the need for the development of greenhouse gas sensors for climatic usage by using selected examples. Full article

The wastewater of the industrial production of artificial sweetener sucralose contained an average 1100 mg/L of total organic carbon (TOC) with 2100 mg/L of chemical oxygen demand and 10 mg/L of biological oxygen demand. Biodegradability of the wastewater components was low due to chlorinated organic substances. The combined chemical and biological treatment of this wastewater in the bioreactors with hematite iron ore removed up to 70% of TOC. About 20% of TOC was removed quickly by adsorption on iron ore particles, but adsorption/precipitation of others up to 50% of TOC was due to ferrous/ferric ions and hydroxides produced during microbial reduction and dissolution of iron ore. The calculated dosage of iron ore with 150 regeneration cycles could be 46.7 g/L of wastewater. Thus, the treatment of wastewater with iron ore and iron-reducing bacteria diminished the quantity of granulated activated carbon that is used in the treatment of sucralose production wastewater by up to 70%. Full article

The ongoing research and development of sunlight-driven water splitting in the “Japan Technological Research Association of Artificial Photosynthetic Chemical Process (ARPChem)” is overviewed. Water splitting photocatalysts, photoelectrochemical devices, large-scale reactor panels, product gas transportation, H₂/O₂ gas separation devices and safety measures against explosion are included as the research objectives. ARPChem was formed as a research union of Japan’s leading chemical firms, in which related elementary technologies have been cultivated. This article introduces our general scope for artificial photosynthesis and describes present research activities, mainly on solar driven water splitting photocatalysts/photoelectrodes and briefly on the processes and plans for plant construction for future industrial extension. Full article

An agricultural residue, white yam (Dioscorea rotundata) tuber peel (YTBS), was used for the removal of Cd(II) ion from an aqueous solution using a batch method. The adsorbent was characterized using FTIR, TGA, SEM, EDX, N₂ BET, XRD, and XRF. The optimization of sorption variables such as pH, contact time, adsorbent dose, and initial metal ion concentration at 25 °C were also carried out. The results indicated the dependence of sorption on the adsorbate pH and adsorbent dose, while the adsorption system reached equilibrium in 180 min. The sorption kinetics was fitted to three models (pseudo first order, pseudo second order, and Elovich) to validate the kinetics, and the pseudo first order was the best model for the description of Cd(II) uptake. Equilibrium isotherm modelling was also carried out using the Langmuir, Freundlich, and Temkin models, with the Langmuir isotherm giving the best fitting to the experimental results. The maximum loading capacity (q_max) of the adsorbent for Cd(II) obtained from the Langmuir isotherm model was 22.4 mg∙g⁻¹ with an isotherm constant (K_L) of 3.46 × 10⁻³ L·mg⁻¹ and r² value of 0.99. This result indicates that the YTBS residue was a good adsorbent for the removal of Cd(II) ion from aqueous system. Full article