ChemEngineering

The heavy-metal-free photocatalytic system, in which carbon nitride is coated on polylactic acid (PLA) as biodegradable plastic through a simple dip coating method, was used for dye decomposition under visible light irradiation. Solvent selection, solvent concentration, and the number of coatings for dip coating were investigated to optimize the conditions for loading carbon nitride on PLA. Carbon nitride cannot be coated on PLA in water, but it can be strongly coated by decomposing the surface of PLA with ethanol or chlorobenzene to promote physical adsorption and activate surface. The number of dip coatings also affected the photocatalytic decomposition ability. The photocatalytic system was able to decompose the dye continuously in the flow method, and dye (rhodamine B) was decomposed by about 50% at a residence time of 12 min (flow rate 0.350 mL/min) for 30 h. Full article

Natural clinoptilolite was studied to assess its performance in removing caesium and strontium ions, using both static columns and an agitated tube reactor (ATR) for process intensification. Kinetic breakthrough curves were fitted using the Thomas and Modified Dose Response (MDR) models. In the static columns, the clinoptilolite adsorption capacity (q_e) for 200 ppm ion concentrations was found to be ~171 and 16 mg/g for caesium and strontium, respectively, highlighting the poor material ability to exchange strontium. Reducing the concentration of strontium to 100 ppm, however, led to a higher strontium q_e of ~48 mg/g (close to the maximum adsorption capacity). Conversely, halving the column residence time to 15 min decreased the q_e for 100 ppm strontium solutions to 13–14 mg/g. All the kinetic breakthrough data correlated well with the maximum adsorption capacities found in previous batch studies, where, in particular, the influence of concentration on the slow uptake kinetics of strontium was evidenced. For the ATR studies, two column lengths were investigated (of 25 and 34 cm) with the clinoptilolite embedded directly into the agitator bar. The 34 cm-length system significantly outperformed the static vertical columns, where the adsorption capacity and breakthrough time were enhanced by ~30%, which was assumed to be due to the heightened kinetics from shear mixing. Critically, the increase in performance was achieved with a relative process flow rate over twice that of the static columns. Full article

In this work volume-translated Peng–Robinson group contribution equation of state was used to calculate excess enthalpies. Four model systems were selected with the purpose to compare experimental and predicted enthalpy values at different temperatures. After the calculations were performed in Matlab software, results were verified with free software tool of Dortmunder Datenbank (DDB). In a next step, the mixing process and interaction forces were described on the basis of the sign and course of enthalpy values. The endothermic behavior of three systems could be well predicted, while for the most polar system, predictions were less precise. Furthermore, the discrepancy between experimental data from the literature and predicted values was discussed to evaluate the accuracy of the selected model. Lowest mean deviations (<75 J/mol and <15% at all temperatures) could be stated for alkane/benzene mixtures, while highest deviations could be again observed for the most polar mixture. Although the magnitude of deviations was in agreement with the literature, it could be shown that the selected temperature is of major importance for the quality of predictions. Furthermore, a review of different literature values for the n-hexane/benzene system could reveal that the reliability of experimental data has to be carefully checked. Full article

Properties of emulsions such as stability, viscosity or color can be influenced by the droplet size distribution. High-pressure homogenization (HPH) is the method of choice for emulsions with a low to medium viscosity with a target mean droplet diameter of less than 1 µm. During HPH, the droplets of the emulsion are exposed to shear and extensional stresses, which cause them to break up. Ongoing work is focused on better understanding the mechanisms of droplet breakup and relevant parameters. Since the gap dimensions of the disruption unit (e.g., flat valve or orifice) are small (usually below 500 µm) and the droplet breakup also takes place on small spatial and time scales, the resolution limit of current measuring systems is reached. In addition, the high velocities impede time resolved measurements. Therefore, a five-fold and fifty-fold magnified optically accessible coaxial orifice were used in this study while maintaining the dimensionless numbers characteristic for the droplet breakup (Reynolds and Weber number, viscosity and density ratio). Three matching material systems are presented. In order to verify their similarity, the local velocity profiles of the emerging free jet were measured using both a microparticle image velocimetry (µ-PIV) and a particle image velocimetry (PIV) system. Furthermore, the influence of the outlet geometry on the velocity profiles is investigated. Similar relationships were found on all investigated scales. The areas with the highest velocity fluctuations were identified where droplets are exposed to the highest turbulent forces. The Reynolds number had no influence on the normalized velocity fluctuation field. The confinement of the jet started to influence the velocity field if the outlet channel diameter is smaller than 10 times the diameter of the orifice. In conclusion, the scaling approach offers advantages to study very fast processes on very small spatial scales in detail. The presented scaling approach also offers chances in the optimization of the geometry of the disruption unit. However, the results also show challenges of each size scale, which can come from the respective production, measurement technology or experimental design. Depending on the problem to be investigated, we recommend conducting experimental studies at different scales. Full article

Laponite is an artificial nanoclay available in large quantities and at low cost. This marterial represents an efficient and suitable way of delivering hydrophobic vital dyes without the need for chemical functionalization. Laponite is available in large quantities and at low cost, then it would be an efficient way of delivering hydrophobic vital dyes without the need for chemical functionalization. The hydrodynamic diameter of laponite extrapolated to infinite dilution indicates that this clay is completely exfoliated. Furthermore, the hydrodynamic diameter in the laponite-Indocyanine green-water ternary system, at a fixed laponite concentration (2% (m/m)) exhibits a saturation curve. It was found that the extrapolated diameter at dye zero concentration is smaller than in pure water. Absorption spectra with fixed concentration of dye exhibit a red shift of 10–13 nm. On the contrary, the spectra acquired at a constant concentration of laponite do not undergo any displacement. The deconvolution of the spectra with two Gaussian peaks allows to calculate the concentration of the monomeric and dimeric species. The results were interpreted as a synergy between the dye dimerization balance and the dye-laponite binding. Full article

Three new uranyl sulfates, [pyH](H₃O)[(UO₂)₃(SO₄)₄(H₂O)₂] (1), [pyH]₂[(UO₂)₆(SO₄)₇(H₂O)] (2), and [pyH]₂[(UO₂)₂(SO₄)₃] (3), were produced upon hydrothermal treatment and successive isothermal evaporation. 1 is monoclinic, P2₁/c, a = 14.3640(13), b = 10.0910(9), c = 18.8690(17) Å, β = 107.795(2), V = 2604.2(4) ų, R₁ = 0.038; 2 is orthorhombic, C222₁, a = 10.1992(8), b = 18.5215(14), c = 22.7187(17) Å, V = 4291.7(6) ų, R₁ = 0.030; 3 is orthorhombic, Pccn, a = 9.7998(8), b = 10.0768(8), c = 20.947(2) Å, V = 2068.5(3) ų, R₁ = 0.055. In the structures of 1 and 2, the uranium polyhedra and SO₄ tetrahedra share vertices to form ${}_{\infty }^3$[(UO₂)₃(SO₄)₄(H₂O)₂]²⁻ and ${}_{\infty }^3$[(UO₂)₆(SO₄)₇(H₂O)]²⁻ frameworks featuring channels (12.2 × 6.7 Å in 1 and 12.9 × 6.5 Å in 2), which are occupied by pyridinium cations. The structure of 3 is comprised of ${}_{\infty }^2$[(UO₂)₂(SO₄)₃]²⁻ layers linked by hydrogen bonds donated by pyridinium cations. The compounds 1–3 are formed during recrystallization processes, in which the evaporation of mother liquor leads to a stepwise loss of hydration water. Full article

In this paper we analyse static properties of mass spring models (MSMs) with the focus of modelling non crystalline materials, and explore basic improvements, which can be made to MSMs with disordered point placement. Presented techniques address the problem of high variance of MSM properties which occur due to randomised nature of point distribution. The focus is placed on tuning spring parameters in a way which would compensate for local non-uniformity of point and spring density. We demonstrate that a simple force balancing algorithm can improve properties of the MSM on a global scale, while a more detailed stress distribution analysis is needed to achieve local scale improvements. Considered MSMs are three dimensional. Full article

This paper addresses the issues of slug detection and characterization in air-water two-phase flow in a vertical pipeline. A novel non-invasive measurement technique using continuous-wave Doppler ultrasound (CWDU) and bandpass power spectral density (BPSD) is proposed for multiphase flow applications and compared with the more established gamma-ray densitometry measurement. In this work, analysis using time-frequency analysis of the CWDU is performed to infer the applicability of the BPSD method for observing the slug front and trailing bubbles in a multiphase flow. The CWDU used a piezo transmitter/receiver pair with an ultrasonic frequency of 500 kHz. Signal processing on the demodulated signal of Doppler frequency was done using the Butterworth bandpass filter on the power spectral density which reveals slugs from background bubbles. The experiments were carried out in the 2” vertical pipeline-riser at the process system engineering laboratory at Cranfield University. The 2-inch test facility used in this experiment is made up of a 54.8 mm internal diameter and 10.5 m high vertical riser connected to a 40 m long horizontal pipeline. Taylor bubbles were generated using a quick-closing air valve placed at the bottom of the riser underwater flow, with rates of 0.5 litres/s, 2 litres/s, and 4 litres/s. The CWDU spectrum of the measured signal along with the BPSD method is shown to describe the distinctive nature of the slugs. Full article

Pathogenic bacteria and other microorganisms pose a potent threat to humans by causing various infectious diseases. To control the spread of infection, different antibacterial products have been developed. However, most of them are known to be associated with health hazards, environmental pollution, complex fabrication, and/or higher cost. To address these issues, in this study, a low cost, biodegradable and human skin compatible antibacterial paper has been developed. A quaternary ammonium compound, benzalkonium chloride (BKC) has been used for paper surface treatment. The concentration of aqueous solution of BKC coated on paper was varied from 0.1 wt% to 0.2 wt%. No external binder was required for coating BKC onto paper. The efficacy of the coated paper was investigated against Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 8739 bacterial strains. This antibacterial paper is highly effective against both strains with the concentrations of BKC being within the allowable limit for cytotoxic effects. The optimum concentration of BKC coated on paper can be considered as 0.15 wt%, as nearly 100% inhibition was achieved with it against both strains. The developed antibacterial paper is suitable for being used in the industry for disinfection and food packaging purposes, and also by the public for hand sanitization. Full article

The present study deals with the relation between crystalline order in kaolinites and their ability to intercalate DMSO. Raw clays and kaolinite–DMSO complexes are analyzed using FTIR, XRD powder diffraction and differential scanning calorimetry and thermogravimetric analysis (DSC-TGA). The crystallinity is accessed using the Hinckley index (HI) from the raw clays’ XRD patterns and the p₂ factor from their FTIR spectra. The intercalation ratio is evaluated from XRD and compared among the samples. The thermal analyses show a decrease in the dehydroxylation temperature in the DMSO–kaolinite complexes, indicating a decrease in the interlayer cohesion that may be useful to improve the delamination of kaolinite. The analysis of the coherent scattering domain size in the raw and the DMSO-intercalated samples indicates that the ordering is not affected during the DMSO intercalation. From these results, it is deduced that DMSO intercalation is favored by an increased crystallinity, as revealed by the intercalation ratio from XRD and the DSMO release during DSC-TGA analysis. Full article

Coal gasification is a new direction for the clean utilization of coal, but it also brings huge environmental pressure on solid waste. In this paper, the high-crystallinity single-phase zeolite A was prepared by solid-phase alkali fusion synthesis from coal gasification fine slag (CGFS), without template agent, with low water consumption, and with low cost, and it was used to remove heavy metals such as Pb²⁺ and Cu²⁺ in simulated waste water. The main factors affecting the solid-phase and green synthesis methods were analyzed, and the optimum conditions for solid-phase synthesis of high-crystallinity single-phase zeolite A were determined as follows: NaOH/CGFS = 1.2; solid-phase alkali fusion temperature 823 K, solid-phase alkali fusion 90 min, liquid–solid ratio 4.5, and 353 K hydrothermal reaction for 12 h. The relative crystallinity, specific surface area, and ion-exchange capacity of single-phase zeolites A are 93.1%, 61.09 m²/g, and 268.4 mmol/100 g. The removal rates of Pb²⁺ and Cu²⁺ can reach more than 99%, especially for the removal efficiency of Pb²⁺, which is common in simulated waste water. This is an effective method with important application prospects, and it formed an effective way to recycle solid waste of coal chemical industry. Full article

High-pressure homogenizers (HPH) equipped with a Simultaneous Homogenization and Mixing (SHM) orifice allow for inducing a mixing stream directly into the disruption unit. Previous studies show that by doing so, synergies between the unit operations “emulsification” and “mixing” can be used to save energy, e.g., in homogenization of dairy products, or to extend the application range of HPH. Up to now, process design has mainly been based on the trial and error principle due to incomplete understanding of flow conditions and droplet break-up in the SHM unit. This study aims at a higher level of understanding of cavitation and mixing effects on emulsion droplet size. Experimental data were obtained using a model emulsion of low disperse phase concentration in order to avoid coalescence effects. The different flow conditions are created by varying the process and geometric parameters of an SHM unit. The results show that the oil droplet size only depends on mixing conditions when the emulsion droplets are added in the mixing stream. Furthermore, a smaller oil droplet size can be achieved by reducing cavitation, especially for droplets fed in the high-pressure stream. Full article

This paper starts with short descriptions of emulsion preparation methods used at large and smaller scales. We give scaling relations as they are generally used, and focus on the central role that interfacial tension plays in these relations. The actual values of the interfacial tension are far from certain given the dynamic behavior of surface-active components, and the lack of measurement methods that can be applied to conditions as they occur during large-scale preparation. Microfluidic techniques are expected to be very instrumental in closing this gap. Reduction of interfacial tension resulting from emulsifier adsorption at the oil-water interface is a complex process that consists of various steps. We discuss them here, and present methods used to probe them. Specifically, methods based on microfluidic tools are of great interest to study short droplet formation times, and also coalescence behavior of droplets. We present the newest insights in this field, which are expected to bring interfacial tension observations to a level that is of direct relevance for the large-scale preparation of emulsions, and that of other multi-phase products. Full article

The realistic numerical simulation of chemical processes, such as those occurring in catalytic reactors, is a complex undertaking, requiring knowledge of chemical thermodynamics, multi-component activated rate equations, coupled flows of material and heat, etc. A standard approach is to make use of a process simulation program package. However for a basic understanding, it may be advantageous to sacrifice some realism and to independently reproduce, in essence, the package computations. Here, we set up and numerically solve the basic equations governing the functioning of plug-flow reactors (PFR) and continuously stirred tank reactors (CSTR), and we demonstrate the procedure with simplified cases of the catalytic hydrogenation of carbon dioxide to form the synthetic fuels methanol and methane, each of which involves five chemical species undergoing three coupled chemical reactions. We show how to predict final product concentrations as a function of the catalyst system, reactor parameters, initial reactant concentrations, temperature, and pressure. Further, we use the numerical solutions to verify the “thermodynamic limit” of a PFR and a CSTR, and, for a PFR, to demonstrate the enhanced efficiency obtainable by “looping” and “sorption-enhancement”. Full article

Structured open-cell foam reactors are promising for managing highly exothermic reactions such as CO₂ methanation due to their excellent heat transport properties. Especially at low flow rates and under dynamic operation, foam-based reactors can be advantageous over classic fixed-bed reactors. To efficiently design the catalyst carriers, a thorough understanding of heat transport mechanisms is needed. So far, studies on heat transport in foams have mostly focused on the solid phase and used air at atmospheric pressure as fluid phase. With the aid of pore-scale 3d CFD simulations, we analyze the effect of the fluid properties on heat transport under conditions close to the CO₂ methanation reaction for two different foam structures. The exothermicity is mimicked via volumetric uniformly distributed heat sources. We found for foams that are designed to be used as catalyst carriers that the working pressure range and the superficial velocity influence the dominant heat removal mechanism significantly. In contrast, the influence of fluid type and gravity on heat removal is small in the range relevant for heterogeneous catalysis. The findings might help to facilitate the design-process of open-cell foam reactors and to better understand heat transport mechanisms in foams. Full article

For the research on droplet deformation and breakup in scaled high-pressure homogenizing units, a pressure stable inline droplet generator was developed. It consists of an optically accessible flow channel with a combination of stainless steel and glass capillaries and a 3D printed orifice. The droplet size is determined online by live image analysis. The influence of the orifice diameter, the mass flow of the continuous phase and the mass flow of the disperse phase on the droplet diameter were investigated. Furthermore, the droplet detachment mechanisms were identified. Droplet diameters with a small diameter fluctuation between 175 µm and 500 µm could be realized, which allows a precise adjustment of the capillary (Ca) and Weber (We) Number in the subsequent scaled high pressure homogenizer disruption unit. The determined influence of geometry and process parameters on the resulting droplet size and droplet detachment mechanism agreed well with the literature on microfluidics. Furthermore, droplet trajectories in an exemplary scaled high-pressure homogenizer disruption unit are presented which show that the droplets can be reinjected on a trajectory close to the center axis or close to the wall, which should result in different stresses on the droplets. Full article

The objective of this article is to provide an overview on the current development of micro- and nanoporous fiber processing and manufacturing technologies. Various methods for making micro- and nanoporous fibers including co-electrospinning, melt spinning, dry jet-wet quenching spinning, vapor deposition, template assisted deposition, electrochemical oxidization, and hydrothermal oxidization are presented. Comparison is made in terms of advantages and disadvantages of different routes for porous fiber processing. Characterization of the pore size, porosity, and specific area is introduced as well. Applications of porous fibers in various fields are discussed. The emphasis is put on their uses for energy storage components and devices including rechargeable batteries and supercapacitors. Full article