Chemical and Process Engineering: New Frontiers

Ozonation is a heterogeneous process of chemical absorption often controlled by a gas-liquid mass transfer rate. This paper presents the results of kinetics in a reaction between phenylphenol isomers and ozone. The degradation of phenylphenol isomers during ozonation proceeds quite fast. In order to avoid the influence of mass transfer limitation the kinetics experiments were conducted in a homogenous liquid-liquid system. The second-order rate constants were determined using classical and competition methods, which are especially recommended for fast reactions. The determined rate constants at pH 2 using the two different methods are almost the same. The increase of pH causes an increase of rate constants for the reaction of phenylphenol isomers with ozone.

The enzymatic synthesis of a highly hydrophobic product (dipeptide precursor) in which the reaction is accompanied by the mass transfer of the reaction product to the organic phase and the substrates to the water phase is considered. Equations describing both continuous and batch processes are formulated. The range of variability in the operating parameters of such a bioreactor is specified, and the correlations reported in the literature to describe mass transfer in the membrane contactor are validated. The proposed process was verified experimentally, and good agreement between the determined and calculated concentrations was obtained in both phases.

The fixation of CO2 in the form of inorganic carbonates, also known as mineral carbonation, is an interesting option for the removal of carbon dioxide from various gas streams. The captured CO2 is reacted with metal-oxide bearing materials, usually naturally occurring minerals. The alkaline industrial waste, such as fly ash can also be considered as a source of calcium or magnesium. In the present study the solubility of fly ash from conventional pulverised hard coal fired boilers, with and without desulphurisation products, and fly ash from lignite fluidised bed combustion, generated by Polish power stations was analysed. The principal objective was to assess the potential of fly ash used as a reactant in the process of mineral carbonation. Experiments were done in a 1 dm3 reactor equipped with a heating jacket and a stirrer. The rate of dissolution in water and in acid solutions was measured at various temperatures (20 - 80ºC), waste-to-solvent ratios (1:100 - 1:4) and stirrer speeds (300 - 1100 min-1). Results clearly show that fluidised lignite fly ash has the highest potential for carbonation due to its high content of free CaO and fast kinetics of dissolution, and can be employed in mineral carbonation of CO2.

A comparative analysis concerning the influence of different factors on momentum transfer in mechanically agitated systems was carried out on the basis of experimental results for solid-liquid, gas-liquid and gas-solid-liquid systems. The effects of the impeller - baffles system geometry, scale of the agitated vessel, type and number of impellers and their off-bottom clearance, as well as physical properties of the multiphase systems on the critical impeller speeds needed to produce suspension or dispersion, power consumption and gas hold-up were analysed and evaluated.

The paper presents an investigation of mass transfer in gas-liquid annular flow in a microreactor. The microreactor had a meandered shape with a square cross-section of the channel (292×292 μm, hydraulic diameter 292 μm) and 250 mm in length. The rate of CO2 absorption from the CO2/N2 mixture in NaOH (0.1 M, 0.2 M, 0.7 M, 1.0 M and 1.5 M) water solutions was measured. Two velocities of gas flow and two velocities of liquid flow were used. In two cases a fully developed annular flow at the beginning of the channel was observed, whilst in two cases annular flow was formed only in about 2/3 of the microchannel length. Based on the measurements of CO2 absorption rate, the values of volumetric liquid - side mass transfer coefficients with the chemical reaction were determined. Then physical values of coefficients were found. Obtained results were discussed and their values were compared with the values predicted by literature correlations.

In this study the authors minimise the total process cost for the heating of solid particles in a horizontal fluidised bed by an optimal choice of the inlet heating gas temperature profile and the total gas flow. Solid particles flowed along the apparatus and were heated by a hot gas entering from the bottom of the fluidised apparatus. The hydrodynamics of the fluidised bed is described by a two-phase Kunii - Levenspiel model. We assumed that the gas was flowing only vertically, whereas solid particles were flowing horizontally and because of dispersion they could be additionally mixed up in the same direction. The mixing rate was described by the axial dispersion coefficient. As any economic values of variables describing analysing process are subject to local and time fluctuations, the accepted objective function describes the total cost of the process expressed in exergy units. The continuous optimisation algorithm of the Maximum Principle was used for calculations. A mathematical model of the process, including boundary conditions in a form convenient for optimisation, was derived and presented. The optimization results are presented as an optimal profile of inlet gas temperature. The influence of heat transfer kinetics and dispersion coefficients on optimal runs of the heating process is discussed. Results of this discussion constitute a novelty in comparison to information presented in current literature.

Chitin deacetylase is the only known enzyme which is able to deacetylate N-acetyl-D-glucosamine units in chitin or chitosan chains. As chitin can hardly be dissolved in organic/inorganic solvents, new solvents are still searched. Ionic liquids are promising for that application and for homophase enzymatic deacetylation. The aim of the work was to investigate the influence of selected ionic liquids on activity of chitin deacetylase.

It has been shown that [Amim] ionic liquids increase the activity of chitin deacetylase. The highest activity was observed for [Amim][Cl]. Ionic liquids with shorter (ethyl (C2)) and longer side chain (buthyl (C4)) only insignificantly influenced the activity of the enzyme. All tested ionic liquids with [Br] anion increased the activity of chitin deacetylase while the [Emim] and [Bmim] cation in combination with [Cl] anion inhibited the activity of the enzyme.

In the paper the results of measurements of CO2 absorption rate in aqueous potassium carbonate solutions containing cyclohexylamine, diethanolamine, 2-methylaminoethanol and triethylenetetramine as activators have been presented. Enhnancement mass transfer factors as well as reaction rate constants have been determined. Results show that among the tested activators triethylenetetramine and 2-methyl-aminoethanol may be used (instead of diethanolamine) as new promotors in a modified BENFLIELD process.

The aim of the present study was to investigate the sensitivity of a multiphase Eulerian CFD model with respect to relations defining drag forces between phases. The mean relative error as well as standard deviation of experimental and computed values of pressure gradient and average liquid holdup were used as validation criteria of the model. Comparative basis for simulations was our own data-base obtained in experiments carried out in a TBR operating at a co-current downward gas and liquid flow. Estimated errors showed that the classical equations of Attou et al. (1999) defining the friction factors Fjk approximate experimental values of hydrodynamic parameters with the best agreement. Taking this into account one can recommend to apply chosen equations in the momentum balances of TBR.

Efforts were made to demonstrate that in biorefineries it is possible to manufacture all the commodities required for maintaining human civilisation on the current level. Biorefineries are based on processing biomass resulting from photosynthesis. From sugars, oils and proteins, a variety of food, feed, nutrients, pharmaceuticals, polymers, chemicals and fuels can further be produced. Production in biorefineries must be based on a few rules to fulfil sustainable development: all raw materials are derived from biomass, all products are biodegradable and production methods are in accordance with the principles of Green Chemistry and Clean Technology. The paper presents a summary of state-of-the-art concerning biorefineries, production methods and product range of leading companies in the world that are already implemented. Potential risks caused by the development of biorefineries, such as: insecurities of food and feed production, uncontrolled changes in global production profiles, monocultures, eutrophication, etc., were also highlighted in this paper. It was stressed that the sustainable development is not only an alternative point of view but is our condition to survive.

In this work the esterification of diethyl tartrate was studied. The research was focused on the enhancement of reversible reaction yield, which is accomplished by dewatering of the reaction mixture. The removal of water shifts the equilibrium towards the main product. Pervaporation was applied for this purpose, and results were compared to distillation. The advantages and limitations of both processes are discussed. The experimental part consists of dewatering of mixture after the reaction had reached the equilibrium, and was subsequently fed to the test rig equipped with a single zeolite membrane purchased from Pervatech B.V. Results show a significant conversion increase as a result of water removal by pervaporation. Compared to distillation no addition of organics is necessary to efficiently remove water above the azeotrope. Nevertheless, some limitations and issues which call for optimisation are pointed out. A simple numerical model is proposed to support design and sizing of the pervaporation system. Various modes of integrated system operation are also briefly discussed.

Liquid-liquid extraction provides an environmentally friendly process as an alternative to azeotropic distillation, pervaporation and reverse osmosis because these techniques require the use of large amounts of energy, may involve volatile organic compounds, and operation at high pressure.

Ionic liquids (ILs) continue to gain wide recognition as potential environmentally friendly solvents due to their unique properties. However due to their current high cost, their use in industry is seriously limited without an efficient methodology for recovery and recycle.

In this paper we describe an innovative methodology for a liquid-liquid extraction process based on an electrically induced emulsion of an ionic liquid as the extracting solvent dispersed in an organic mixture. This offers a most efficient exploitation of the solvent. On the other hand we present our own design of a pilot (semi-industrial) scale extractor based on this methodology and which demonstrates effective recovery of the ionic liquid. In order to achieve this goal we used a numerical modelling tool implemented using our own simulation software based on the finite element method. We also used our original previous experience with generating and investigating liquid-liquid electrosprays using phase Doppler anemometry. Finally we present recommendations for contactor geometry and for the preferred operating conditions for the extractor.

A mathematical model of a hybrid culture system supported with a stationary layer of liquid perfluorochemical (PFC) as a source of O2 for cells which grow in the aqueous phase of culture medium has been developed and discussed. The two-substrate Monod kinetics without inhibition effects, i.e. the Tsao-Hanson equation, has been assumed to characterise the biomass growth. The Damköhler number which relates the growth rate to the mass transfer effects has been used to appraise the regime (i.e. diffusion-limited or kinetics) of the whole process. The proposed model predicted accurately previously published data on the submerged batch cultures of Nicotiana tabacum BY-2 heterotrophic cells performed in a culture system supported with a stationary layer of hydrophobic perfluorodecalin as a liquid O2 carrier. Estimated values of the parameters of the model showed that the process proceeded in the kinetics regime and the growth kinetics, not the effects of the mass transfer between aqueous phase and liquid PFC, had essential influence on the growth of biomass.