Chemical and Process Engineering: New Frontiers

A simple analytical method for determination of basic hydrodynamic characteristics of hybrid fluidized-bed air-lift devices was presented. These devices consist of two parts: a two-phase air-lift part and a two-phase liquid-solid fluidized-bed part. Forced circulation of fluid in the air-lift part is used for fluidization of solid particles in the fluidized-bed part. According to the opinion given in the literature, if such apparatus is used for aerobic microbiological processes, its advantage is lower shear forces acting on the biofilm immobilized on fine-grained material compared with shear forces in three-phase fluidized-bed bioreactors. Another advantage is higher biomass concentration due to its immobilization on fine particles, compared with two-phase airlift bioreactors. A method of calculating gas hold-up in the air-lift part, and gas and liquid velocities in all zones of the analyzed apparatus is presented.

Experimental investigations and numerical simulations have been conducted in this study to derive and test the values of kinetic parameters describing oxidation and gasification reactions between char carbon and O2 and CO2 occurring at standard air and oxy-fuel combustion conditions. Experiments were carried out in an electrically heated drop-tube at heating rates comparable to fullscale pulverized fuel combustion chambers. Values of the kinetic parameters, obtained by minimization of the difference between the experimental and modeled values of char burnout, have been derived and CFD simulations reproducing the experimental conditions of the drop tube furnace confirmed proper agreement between numerical and experimental char burnout.

Aerosol filtration in fibrous filters is one of the principal methods of accurate removal of particulate matter from a stream of gas. The classical theory of depth filtration of aerosol particles in fibrous structures is based on the assumption of existing single fibre efficiency, which may be used to recalculate the overall efficiency of entire filter. Using “classical theory” of filtration one may introduce some errors, leading finally to a discrepancy between theory and experiment. There are several reasons for inappropriate estimation of the single fibre efficiency: i) neglecting of shortrange interactions, ii) separation of inertial and Brownian effects, ii) perfect adhesion of particles to the fibre, iv) assumption of perfect mixing of aerosol particles in the gas stream, v) assumption of negligible effect of the presence of neighbouring fibres and vi) assumption of perpendicular orientation of homogenous fibres in the filtration structure. Generally speaking, “classical theory” of filtration was used for characterization of the steady - state filtration process (filtration in a clean filter, at the beginning of the process) without deeper investigation of the influence of the nternal structure of the filter on its performance. The aim of this review is to outline and discuss the progress of deep-bed filtration modelling from the use of simple empirical correlations to advanced techniques of Computational Fluid Dynamics and Digital Fluid Dynamics.

Results of laboratory scale research have been presented on the effects of an oxidizing reactor on ozone consumption and by-producs composition and separation of simultaneous NOx and SO2 removal from a carrier gas by ozonation method and absorption in an alkaline solution. The additional Dreschel washer added before two washers containing 100 ml of 0.1 molar NaOH solution played the role of an oxidation reactor. Its effect was investigated using an empty (dry or wetted) or filled with packing elements washer. The measured by-products in a scrubber and in the oxidizing reactor were SO32-, SO42-, NO2- and NO3- ions, respectively. It has been shown that use of oxidizing reactor improves NOx removal efficiency reducing ozone consumption. Wetting of the oxidation reactor with water enables a preliminary separation of sulphur and nitrogen species between the oxidizing reactor and an alkaline absorber. Application of packing elements in the oxidizing reactor allows to retain 90% of nitrogen compounds in it. Some results were confirmed by tests in pilot scale.

Hydrogen is the fuel of the future, therefore many hydrogen production methods are developed. At present, fuel cells are of great interest due to their energy efficiency and environmental benefits. A brief review of effective formation methods of hydrogen was conducted. It seems that hydrogen from steam reforming of methanol process is the best fuel source to be applied in fuel cells. In this process Cu-based complex catalysts proved to be the best. In presented work kinetic equations from available literature and catalysts are reported. However, hydrogen produced even in the presence of the most selective catalysts in this process is not pure enough for fuel cells and should be purified from CO. Currently, catalysts for hydrogen production are not sufficiently active in oxidation of carbon monoxide. A simple and effective method to lower CO level and obtain clean H2 is the preferential oxidation of monoxide carbon (CO-PROX). Over new CO-PROX catalysts the level of carbon monoxide can be lowered to a sufficient level of 10 ppm.

Thermodynamic principles for the dissolution of gases in ionic liquids (ILs) and the COSMO-SAC model are presented. Extensive experimental data of Henry’s law constants for CO2, N2 and O2 in ionic liquids at temperatures of 280-363 K are compared with numerical predictions to evaluate the accuracy of the COSMO-SAC model. It is found that Henry’s law constants for CO2 are predicted with an average relative deviation of 13%. Both numerical predictions and experimental data reveal that the solubility of carbon dioxide in ILs increases with an increase in the molar mass of ionic liquids, and is visibly more affected by the anion than by the cation. The calculations also show that the highest solubilities are obtained for [Tf2N]ˉ. Thus, the model can be regarded as a useful tool for the screening of ILs that offer the most favourable CO2 solubilities. The predictions of the COSMOSAC model for N2 and O2 in ILs differ from the pertinent experimental data. In its present form the COSMO-SAC model is not suitable for the estimation of N2 and O2 solubilities in ionic liquids.

Inexpensive synthesis of electroceramic materials is required for efficient energy storage. Here the design of a scalable process, flame spray pyrolysis (FSP), for synthesis of size-controlled nanomaterials is investigated focusing on understanding the role of air entrainment (AE) during their aerosol synthesis with emphasis on battery materials. The AE into the enclosed FSP reactor is analysed quantitatively by computational fluid dynamics (CFD) and calculated temperatures are verified by Fourier transform infrared spectroscopy (FTIR). Various Li4Ti5O12 (LTO) particle compositions are made and characterized by N2 adsorption, electron microscopy and X-ray diffraction while the electrochemical performance of LTO is tested at various charging rates. Increasing AE decreases recirculation in the enclosing tube leading to lower reactor temperatures and particle concentrations by air dilution as well as shorter and narrower residence time distributions. As a result, particle growth by coagulation - coalescence decreases leading to smaller primary particles that are mostly pure LTO exhibiting high C-rate performance with more than 120 mAh/g galvanostatic specific charge at 40C, outperforming commercial LTO. The effect of AE on FSP-made particle characteristics is demonstrated also in combustion synthesis of LiFePO4 and ZrO2.

A modified emulsion polymerisation synthesis route for preparing highly dispersed cationic polystyrene (PS) nanoparticles is reported. The combined use of 2,2′-azobis[2-(2-imidazolin- 2-yl)propane] di-hydrochloride (VA-044) as the initiator and acetone/water as the solvent medium afforded successful synthesis of cationic PS particles as small as 31 nm in diameter. A formation mechanism for the preparation of PS nanoparticles was proposed, whereby the occurrence of rapid acetone diffusion caused spontaneous rupture of emulsion droplets into smaller droplets. Additionally, acetone helped to reduce the surface tension and increase the solubility of styrene, thus inhibiting aggregation and coagulation among the particles. In contrast, VA-044 initiator could effectively regulate the stability of the PS nanoparticles including both the surface charge and size. Other reaction parameters i.e. VA-044 concentration and reaction time were examined to establish the optimum polymerisation conditions.

Numerical values of the NRTL equation parameters for calculation of the vapour - liquid - liquid equilibria (VLLE) at atmospheric pressures have been presented for 5 ternary mixtures. These values were fitted to the experimental VLLE and vapour - liquid equilibrium (VLE) data to describe simultaneously, as accurately as possible, the VLE and the liquid - liquid equilibria (LLE). The coefficients of this model called further NRTL-VLL were used for simulations of n-propanol dehydration via heterogeneous azeotropic distillation. The calculations performed by a ChemCAD simulator were done for 4 mixtures using hydrocarbons, ether and ester as an entrainer. In majority simulations the top streams of the azeotropic column had composition and temperature similar to the corresponding experimental values of ternary azeotropes. The agreement between the concentrations of both liquid phases formed in a decanter and the experimental values of the LLE was good for all four simulations. The energy requirements were the most advantageous for the simulation with di-npropyl ether (DNPE) and isooctane. Simulations were performed also for one mixture using the NRTL equation coefficients taken from the ChemCAD database. In that case the compositions of the liquid organic phases leaving the decanter differed significantly from the experimental LLE data.

Measurements of dynamic surface tension were carried out in aqueous systems (water or 0.1 mM Triton X-100) comprising nanoparticles formed from chemically modified polyaldehyde dextran (PAD). The nanostructures, considered as potential drug carriers in aerosol therapy, were obtained from biocompatible polysaccharides by successive oxidation and reactive coiling in an aqueous solution. The dynamic surface tension of the samples was determined by the maximum bubble pressure (MBP) method and by the axisymmetric drop shape analysis (ADSA). Experiments with harmonic area perturbations were also carried out in order to determine surface dilatational viscoelasticity. PAD showed a remarkable surface activity. Ward-Tordai equation was used to determine the equilibrium surface tension and diffusion coefficient of PAD nanoparticles (D = 2.3×10-6 m2/s). In a mixture with Triton X-100, PAD particles showed co-adsorption and synergic effect in surface tension reduction at short times (below 10 s). Tested nanoparticles had impact on surface rheology in a mixed system with nonionic surfactant, suggesting their possible interactions with the lung surfactant system after inhalation. This preliminary investigation sets the methodological approach for further research related to the influence of inhaled PAD nanoparticles on the lung surfactant and mass transfer processes in the respiratory system.

In this work a concept of energetic efficiency of mixing is presented and discussed; a classical definition of mixing efficiency is modified to include effects of the Schmidt number and the Reynolds number. Generalization to turbulent flows is presented as well. It is shown how the energetic efficiency of mixing as well as efficiencies of drop breakage and mass transfer in twophase liquid-liquid systems can be identified using mathematical models and test chemical reactions. New expressions for analyzing efficiency problem are applied to identify the energetic efficiency of mixing in a stirred tank, a rotor stator mixer and a microreactor. Published experimental data and new results obtained using new systems of test reactions are applied. It has been shown that the efficiency of mixing is small in popular types of reactors and mixers and thus there is some space for improvement.

Room-temperature ionic liquids (RTILs) are a moderately new class of liquid substances that are characterized by a great variety of possible anion-cation combinations giving each of them different properties. For this reason, they have been termed as designer solvents and, as such, they are particularly promising for liquid-liquid extraction, which has been quite intensely studied over the last decade. This paper concentrates on the recent liquid-liquid extraction studies involving ionic liquids, yet focusing strictly on the separation of n-butanol from model aqueous solutions. Such research is undertaken mainly with the intention of facilitating biological butanol production, which is usually carried out through the ABE fermentation process. So far, various sorts of RTILs have been tested for this purpose while mostly ternary liquid-liquid systems have been investigated. The industrial design of liquid-liquid extraction requires prior knowledge of the state of thermodynamic equilibrium and its relation to the process parameters. Such knowledge can be obtained by performing a series of extraction experiments and employing a certain mathematical model to approximate the equilibrium. There are at least a few models available but this paper concentrates primarily on the NRTL equation, which has proven to be one of the most accurate tools for correlating experimental equilibrium data. Thus, all the presented studies have been selected based on the accepted modeling method. The reader is also shown how the NRTL equation can be used to model liquid-liquid systems containing more than three components as it has been the authors’ recent area of expertise.

This paper presents a study on the effect of cleaning factors on the energy consumption of the cleaning process in a CIP system, and the correlation between single components of electricity necessary to perform this process and the cleanliness degree obtained. Studies were carried out in a laboratory cleaning station, wherein a plate heat exchanger contaminated with hot milk was included. The research program was developed according to a 5-level statistical plan. Based on the results, obtained with Experiment Planner 1.0, a regression function of energy requirement considering variables such as: cleaning time, temperature and flow rate of the cleaning liquid via the cleaned exchanger has been developed. Describing this relationship, linear and quadratic functions with double interactions were used. Significance level for the analysis was established at α = 0.05. Correlation analysis between components of the electricity necessary to perform the cleaning process (pump drive and heating of the cleaning agent) and the resulting degree of cleaning of heat exchanger plates was performed.