Chemical and Process Engineering: New Frontiers

Steady-state characteristics of a catalytic fluidised bed reactor and its dynamical consequences are analyzed. The occurrence of an untypical steady-state structure manifesting in a form of multiple isolas is described. A two-phase bubbling bed model is used for a quantitative description of the bed of catalyst. The influence of heat exchange intensity and a fluidisation ratio onto the generation of isolated solution branches is presented for two kinetic schemes. Dynamical consequences of the coexistence of such untypical branches of steady states are presented. The impact of linear growth of the fluidisation ratio and step change of the cooling medium temperature onto the desired product yield is analyzed. The results presented in this study confirm that the identification of a region of the occurrence of multiple isolas is important due to their strong impact both on the process start-up and its control.

The key feature of thermosensitive polymers is the reversible transition between the hydrophilic and hydrophopic forms depending on the temperature. Although the main research efforts are focused on their application in different kinds of drug delivery systems, this phenomenon also allows one to precisely control the stability of solid-liquid dispersions. In this paper research on the application of poly(N-isopropylacrylamide) copolymers in processing of minerals is presented. In the experiments tailings from flotation plant of one of the coal mines of Jastrzębska Spółka Węglowa S.A. (Poland) were used. A laser particle sizer Fritsch Analysette 22 was used in order to determine the Particle Size Distribution (PSD). It was proved that there are some substantial issues associated with the application of thermosensitive polymers in industrial practice which may exclude them from the common application. High salinity of suspension altered the value of Lower Critical Solution Temperature (LCST). Moreover, the co-polymers used in research proved to be efficient flocculating agents without any temperature rise. Finally, the dosage needed to achieve steric stabilization of suspension was greatly beyond economic justification.

The main objective of these experiments was to study the oxygen mass transfer rate through the volumetric mass transfer coefficient (kLa) for an experimental set-up equipped with a rotating magnetic field (RMF) generator and various liquids. The experimental results indicated that kLa increased along the magnetic strength and the superficial gas velocity. Mathematical correlations defining the influence of the considered factors on kLa were proposed.

Foam fractionation process for concentration of laccases from two Basidiomycete strains under different process conditions was investigated. Culture supernatants of Cerrena unicolor and Pleurotus sapidus containing active laccase were used with and without surfactant additives. Two surfactants: cationic cetrimonium bromide (CTAB) and non-ionic Polysorbate 80 were applied in the range from 0.2 mM to 1.5 mM. The pH levels ranging from 3 to 10 were examined with particular attention to pH=4, which is close to the pI of the enzymes. Results show that the source of the enzyme is significant in terms of partitioning efficiency in a foam fractionation process. Laccase from Cerrena unicolor showed the best activity partitioning coefficients between foamate and retentate of almost 200 with yields reaching 50% for pH 7.5 and concentration of CTAB cCTAB = 0.5 mM, whereas laccase from Pleurotus sapidus showed partitioning coefficients of up to 8 with 25% yield for pH 4 and cCTAB = 0.5 mM.

A mathematical model of waste tyre pyrolysis process is developed in this work. Tyre material decomposition based on a simplified reaction mechanism leads to main product lumps: noncondensable (gas), condensable (pyrolytic oil) and solid (char). The model takes into account kinetics of heat and mass transfer in the grain of the shredded rubber material as well as surrounding gas phase. The main reaction routes were modelled as the pseudo-first order reactions with a rate constant calculated from the Arrhenius type equation using literature values of activation energy determined for main tyre constituents based on TG/DTG measurements and tuned pre-exponential parameter values obtained by fitting theoretical predictions to the experimental results obtained in our laboratory reactor. The model was implemented within the CFD software (ANSYS Fluent). The results of numerical simulation of the pyrolysis process revealed non-uniformity of sample’s porosity and temperature. The simulation predictions were in satisfactory agreement with the experimentally measured mass loss of the tyre sample during pyrolysis process investigated in a laboratory reactor.

The results of numerical computations concerning momentum transfer processes in an air – biophase – liquid system agitated in a bioreactor equipped with baffles and a Smith turbine (CD 6 impeller) are presented in this paper. The effect of sucrose concentration on the distributions of the velocity of the continuous phase, gas hold-up and the size of gas bubbles in the system was analysed. Simulation results were presented in the form of the contours of the analysed magnitudes. The effect of sucrose concentration on the averaged values (i.e. determined on the basis of local values) of gas hold-up and gas bubbles size was evaluated. The results of the numerical computations of gas hold-up were compared with our own experimental data.

Geometric parameters of a ribbon impeller were optimized on the basis of numerical calculations obtained from the solution of our own 3D/2D hybrid model. The optimization was made taking into account mixing power and homogenization time for ribbon impellers with a different number of ribbons and width operating in a laminar motion for Newtonian fluid. Due to minimum mixing energy required to stir a unit volume of liquid the most efficient impeller appeared to be that with one ribbon of width equal to 0.1 to 0.15 of the mixing vessel diameter. Impellers with more than one ribbon needed much higher mixing power but did not increase significantly secondary circulation in the vessel. These impellers increased first of all primary circulation, i.e. they increased only circular motion of liquid in the vessel.

In this paper, thermal processing of starch slurry in a Couette-Taylor flow (CTF) apparatus was investigated. Gelatinized starch dispersion, after treatment in the CTF apparatus, was characterized using such parameters like starch granule diameters (or average diameter), starch granule swelling degree (quantifying the amount of water absorbed by starch granules) and concentration of dissolved starch. These parameters were affected mostly by the process temperature, although the impact of the axial flow or rotor rotation on them was also observed. Moreover, the analysis of results showed a relatively good correlation between these parameters, as well as, between those parameter and apparent viscosity of gelatinized starch dispersion. Meanwhile, the increase in the value of the apparent viscosity and in shear-tinning behaviour of dispersion was associated with the progress of starch processing in the CTF apparatus. Finally, the CTF apparatuses of different geometries were compared using numerical simulation of the process. The results of the simulation indicated that the apparatus scaling-up without increasing the width of the gap between cylinders results in higher mechanical energy consumption per unit of processed starch slurry.

In many systems of engineering interest the moment transformation of population balance is applied. One of the methods to solve the transformed population balance equations is the quadrature method of moments. It is based on the approximation of the density function in the source term by the Gaussian quadrature so that it preserves the moments of the original distribution. In this work we propose another method to be applied to the multivariate population problem in chemical engineering, namely a Gaussian cubature (GC) technique that applies linear programming for the approximation of the multivariate distribution. Examples of the application of the Gaussian cubature (GC) are presented for four processes typical for chemical engineering applications. The first and second ones are devoted to crystallization modeling with direction-dependent two-dimensional and three-dimensional growth rates, the third one represents drop dispersion accompanied by mass transfer in liquid-liquid dispersions and finally the fourth case regards the aggregation and sintering of particle populations.

A pair of fast competitive reactions, neutralization and 2,2-dimetoxypropane (DMP) hydrolysis, has been applied do study mass transfer and micromixing in a T 50 Ultra-Turrax® - IKA rotor-stator device. In experiments the dispersed organic phase containing p-Toluenesulfonic acid (pTsOH) dissolved in diisopropyl ether, whereas the continuous phase was represented by the aqueous solution of sodium hydroxide, 2,2-dimetoxypropane (DMP) and ethanol. During mixing a fast mass transfer of a solute (pTsOH) from organic phase droplets, which were shrinking due to fast dissolution of the organic solvent, was followed by micromixing and chemical reactions in the continuous phase. Measured hydrolysis yields were applied to express effects of mixing on the course of chemical reactions. Modeling was based on application of models describing drop breakup, mass transfer in the liquid-liquid system and micromixing. Combined effects of mass transfer and drop breakage on drop population were expressed using the population balance equations. The model has been used to interpret experimental results, in particular to identify the efficiency of mixing.

Energetic efficiency depicting the fraction of energy dissipation rate used to perform processes of drop breakup and mass transfer in two-phase, liquid-liquid systems is considered. Results of experiments carried out earlier in two types of high-shear mixers: an in-line rotor-stator mixer and a batch rotor-stator mixer, have been applied to identify and compare the efficiency of drop breakage and mass transfer in both types of mixers. The applied method is based on experimental determination of both: the product distribution of chemical test reactions and the drop size distributions. Experimental data are interpreted using a multifractal model of turbulence for drop breakage and the model by Favelukis and Lavrenteva for mass transfer. Results show that the energetic efficiency of the in-line mixer is higher than that of the batch mixer; two stator geometries were considered in the case of the batch mixer and the energetic efficiency of the device equipped with a standard emulsor screen (SES) was higher than the efficiency of the mixer equipped with a general purpose disintegrating head (GPDH) for drop breakup but smaller for mass transfer.

This paper presents a systematic thermogravimetric (TG) study on the kinetics of end-of-life tyre (ELT) pyrolysis. In the experimental part of this work, TG results are compared for tyre samples of different mass and size. This shows that the conduction resistance in the milligram scale (up to ~100 mg) tyre sample can be neglected. A comparison of experimental results demonstrates that the characteristic maxima on the DTG curve (the first derivative of TG signal) shift towards higher temperatures for higher heating rates. This phenomenon is explained to have kinetic origin and it is not caused by the internal heat transfer resistance. In the modelling part of this work, the kinetic parameters of the Three-Component Simulation Model (TCSM) are calculated and compared to the literature values. Testing of the kinetic model is carried out using experiments with a varying heating rate. This shows the limitation of the simplified kinetic approach and the appropriate selection method of the kinetic parameters.