Chemical and Process Engineering: New Frontiers

The kinetics of the reaction between CO2 and methyldiethanolamine in aqueous solutions have been studied using the stopped-flow technique at 288, 293, 298 and 303 K. The amine concentration ranged from 250 to 875 mol·m-3. The overall reaction rate constant was found to increase with amine concentration and temperature. The acid base catalysis mechanism was applied to correlate the experimentally determined kinetic data. A good agreement between the second order rate constants for the CO2 reaction with MDEA computed from the stopped-flow data and the values reported in the literature was obtained.

In the study a new proposal of convective velocity determination necessary for eddy size determination from the dissipative range in a turbulent flow in a mixer was made. The proposed quantity depends on all the mean and fluctuating velocity components. By applying convective velocity one may determine the distribution of time and linear Taylor microscale in a stirred vessel.

The study was aimed to determine the hydrodynamic of water seepage through a porous bed saturated with different amounts of high viscosity liquids. An attempt was made to describe the process of seepage through beds saturated with oils using the theory of outflow of a liquid from the tank. It was assumed that the discharge coefficient will represent changes of flow resistance during the process. It was found that the dependence of this factor on time is linear. In the second part of this work kinetics of the seepage process was investigated. Dependence of oil concentrations, eluted from the deposit with the flowing water, on time has been evaluated. Thanks to these studies it was possible to determine the effectiveness of an elution of high viscosity liquids from porous beds using water as the washing out liquid.

The effective diffusivity of water in brown coal of Bełchatów mine was experimentally determined. The experiments were performed in superheated steam at 200°C and atmospheric pressure using slightly compressed pellets of cylindrical shape. The drying and temperature curves of the sample were used to identify diffusivity. An inverse problem was formulated and solved by the finite element method for 3D axially symmetric cylindrical geometry of the sample. A satisfactory fit of the simulated curves to experimental results was obtained. The obtained dependence of effective diffusivity on moisture content and temperature may be used in designing lignite dryers.

CFD technique was used to determine the effect of a stent-graft spatial configuration and hematocrit value on blood flow hemodynamic and the risk of a stent-graft occlusion. Spatial configurations of an endovascular prosthesis placed in Abdominal Aortic Aneurysm (AAA) for numerical simulations were developed on the basis of AngioCT data for 10 patients. The results of calculations showed that narrows or angular bends in the prosthesis as well as increased hematocrit affects blood flow reducing velocity and WSS which might result in thrombus development.

The aim of the study was the implementation of a numerical simulation of the air-water two-phase flow in the minichannel and comparing results obtained with the values obtained experimentally. To perform the numerical simulations commercial software ANSYS FLUENT 12 was used. The first step of the study was to reproduce the actual research installation as a three-dimensional model with appropriate and possible simplifications - future computational domain. The next step was discretisation of the computational domain and determination of the types of boundary conditions. ANSYS FLUENT 12 has three built-in basic models with which a two-phase flow can be described. However, in this work Volume-of-Fluid (VOF) model was selected as it meets the established requirements of research. Preliminary calculations were performed for a simplified geometry. The calculations were later verified whether or not the simplifications of geometry were chosen correctly and if they affected the calculation. The next stage was validation of the chosen model. After positive verification, a series of calculations was performed, in which the boundary conditions were the same as the starting conditions in laboratory experiments. A satisfactory description of the experimental data accuracy was attained.

Biosynthesis of lovastatin (a polyketide metabolite of Aspergillus terreus) in bioreactors of different working volume was studied to indicate how the change of scale of the process influences the formation of this metabolite. The experiments conducted in shake flasks of 150 ml working volume allowed to obtain lovastatin titres at the level of 87.5 mg LOV l-1, when two carbon sources, namely lactose and glycerol were used. The application of the same components in a large stirred-tank bioreactor of 5.3-litre working volume caused a decrease of lovastatin production by 87% compared to the shake flask culture. The deficiency of nitrogen in this bioreactor did not favour the formation of lovastatin, in contrast to the small bioreactor of 1.95-litre working volume, in which lovastatin titres comparable to those in the shake flasks could be achieved, when organic nitrogen concentration was two-fold decreased. When the control of pH and/or pO2 was used simultaneously, an increase in lovastatin production was observed in the bioreactors. However, these results were still slightly lower than lovastatin titres obtained in the shake flasks.

Results for microcrystalline cellulose pyrolysis are presented, which includes thermogravimetric measurements and kinetic analysis of experimental data. The effect of sample mass size and heating rate on estimated values of activation energy and pre-exponential factor is demonstrated and a simple modification of procedure is proposed that allows for the correct values of kinetic parameters regardless of the experimental conditions. The efficiency of the proposed method is confirmed for two endothermic chemical reactions. A method of nonlinear regression is used for calculation of kinetic parameters for a single or TG curve or several curves simultaneously.

An analysis of the effect of feed foaming on the efficiency of sunflower oil encapsulation on selected product properties is presented in the paper. Experiments were carried out in a pilot-plant concurrent spray dryer using the gas-admixing technique. The analysis of the product properties showed that the application of foaming makes it possible to control final product properties, e.g. apparent density, bulk density, distribution of particle diameters, etc. at a high efficiency of sunflower oil encapsulation.

In the last decade a growing interest was observed in low-cost adsorbents for heavy metal ions. Clinoptilolite is a mineral sorbent extracted in Poland that is used to remove heavy metal ions from diluted solutions. The experiments in this study were carried out in a laboratory column for multicomponent water solutions of heavy metal ions, i.e. Cu(II), Zn(II) and Ni(II). A mathematical model to calculate the metals' concentration of water solution at the column outlet and the concentration of adsorbed substances in the adsorbent was proposed. It enables determination of breakthrough curves for different process conditions and column dimensions. The model of process dynamics in the column took into account the specificity of sorption described by the Elovich equation (for chemical sorption and ion exchange). Identification of the column dynamics consisted in finding model coefficients β, KE and Deff and comparing the calculated values with experimental data. Searching for coefficients which identify the column operation can involve the use of optimisation methods to find the area of feasible solutions in order to obtain a global extremum. For that purpose our own procedure of genetic algorithm is applied in the study.

The paper presents the results of studies on quartzite milling in a ball mill. The milling was conducted in a batch system, for diversified compositions of balls. The milling product was subjected to granulometrical, morphological and strength analyses. On the basis of the developed Reid's theory and using the Austin-Gardner equation, a form of the function circumscribing the specific rate of comminution of selected size fractions was determined. The values of the breakage rate function bi, j for the mill's apparatus conditions were determined. The impact was investigated for a variable number of grinding media contact points on the values of specific rate S and the values of the breakage rate function bi, j. Furthermore, the values of coefficients occurring in the equations circumscribing the specific rate of milling S and breakage parameter bi, j were determined.

The article focuses on multicomponent system separation with the use of an innovative membrane-based technique i.e. pervaporation. Pervaporation is a membrane technique for separation of liquid mixtures on solid nonporous membranes. Pervaporation is used in this study to separate a quaternary system acetone-butanol-ethanol-water. Such a system may be derived from ABE fermentation process, and the resulting product, biobutanol, is a potential biofuel and may be used in internal combustion engines.

Experiments in the study involving concentration of butanol by pervaporation were performed using PERVAP 4060 flat-sheet commercial membrane. To describe the PV process a semi-empirical approach was used. As a result of experiments and calculations permeance coefficients were obtained. Separation and permeance factors were calculated to assess the efficiency of the system separation. Beforehand, activity coefficients were determined for all the components of the mixture with the NRTL equation. Separation coefficients for all the components differed depending on process parameters: concentration, feed flow rate and process temperature. The study confirmed the separation effect of the quaternary system. The most interesting results were obtained for the concentration of butanol. Pervaporation allows to concentrate butanol over 10 times. The permeance coefficient reached for butanol an average value of 7.06·10-3 in comparison with the results for ethanol 3.24·10-2 and acetone 1.83·10-2 [kmol(m2h)-1]. The temperature change from 50 to 70°C led to an increased permeance factor and there was no apparent effect on it in the feed flow rate. Due to the hydrophobicity of the membrane water fluxes in the quaternary system were negative.

This study was aimed at evaluating the possibility to use the Friedrich-Braun fractional derivative rheological model to assess the viscoelastic properties of xanthan gum with rice starch and sweet potato starch. The Friedrich-Braun fractional derivative rheological model allows to describe viscoelastic properties comprehensively, starting from the behaviour characteristic of purely viscous fluids to the behaviour corresponding to elastic solids. The Friedrich-Braun fractional derivative rheological model has one more virtue which distinguishes it from other models, it allows to determine the relationship between stress and strain and the impact of each of them on viscoelastic properties on the tested material. An analysis of the data described using the Friedrich-Braun fractional derivative rheological model allows to state that all the tested mixtures of starch with xanthan gum form macromolecular gels exhibiting behaviour typical of viscoelastic quasi-solid bodies. The Friedrich-Braun fractional derivative rheological model and 8 rheological parameters of this model allow to determine changes in the structure of the examined starch - xanthan gum mixtures. Similarly important is the possibility to find out the trend and changes going on in this structure as well as their causes.

This paper presents a method for quantitative assessment of the mechanisms of nucleation and granules growth by layering in the process of bed wetting during periodic disc granulation. This study included two initial, consecutive stages of a process with defined time courses. The first phase was a time period, in which only formation of new nuclei took place, while in the second stage simultaneous nucleation and growth of granules as a result of sticking raw material grains to pre-existing nuclei occurred. Different kinds of binding liquid were used for bed wetting in each phase. In the first phase, an aqueous solution of dye was used, and pure distilled water in the second stage. The contribution of particular mechanisms to the formation of agglomerates at different time points within the second phase of the process was determined in this study. To do that the results of bed granulometric analysis, mass balance of size fractions and the analysis of contents of a marker (dye) delivered to the bed with the binding liquid during the first phase in agglomerates were used. To assess the concentration of the dye in different size fractions of the batch, spectrophotometric analysis was utilised. The study was performed using UV-VIS JASCO V-630 spectrophotometer equipped with an integrating sphere. The sieve analysis, spectrophotometric studies and mass balance were used to determine changes in the weight of the dye containing nuclei and of the nuclei containing no dye. The aforementioned analyses were also used to assess changes in the weight of formed granules and of raw material particles attached to nuclei during simultaneous nucleation and growth of granules.

A new concept of an electrostatic spray column for liquid-liquid extraction was investigated. An important problem for separation processes is the presence of azeotropic or close-boiling mixtures in their production, for example heptane with ethanol, since the separation is impossible by ordinary distillation. The use of ionic liquids (IL) as a dispersed solvent specially engineered for any specific organic mixture in terms of selectivity is a key factor to successful separation. As IL present particularly attractive combination of favorable characteristics for the separation of heptane and ethanol, in this work we use 1-butyl-3-methylimidazolium methyl sulfate [BMIM][MeSO4]. Because of high viscosity and relatively high cost of IL a new technique was introduced, consisting in the electrostatically spray generation to enhance the mass transport between the phases. In order to optimally design the geometry of the contactor a series of numerical simulation was performed. Especially multi-nozzle variants for better exploitation of contactor volume were investigated. Experiments showed excellent possibility of control of the dispersion characteristics by applied voltage and thus control of the rate of extraction. The preliminary simulations based on our mathematical model for a three nozzle variant exhibited visual agreement with the theory of electrostatics.

Results of the investigation of thermal degradation of polyolefins in the laboratory-scale set-up reactors are presented in the paper. Melting and cracking processes were carried out in two different types of reactors at the temperature of 390-420°C. This article presents the results obtained for conversion of polyolefin waste in a reactor with a stirrer. Next, they were compared with the results obtained for the process carried out in a reactor with a molten metal bed, which was described in a previous publication. For both processes, the final product consisted of a gaseous (2-16 % mass) and a liquid (84-98 % mass) part. No solid product was produced. The light, "gasoline" fraction of the liquid hydrocarbons mixture (C4-C10) made up over 50% of the liquid product. The overall (vapor) product may be used for electricity generation and the liquid product for fuel production.