Mass transfer in trickle-bed reactors at low reynolds number

Mass transfer rates were determined in a 3.4 cm i.d. trickle-bed reactor in the absence of reaction by absorption measurements and in presence of reaction. Gas flow rates were varied from 0-100 l/h and liquid flow rates from 0-1.5 l/h. The catalyst particles were crushed to an average diameter of 0.054 and 0.09 cm. Mass transfer coefficients remained unaffected by change in gas flow rate but increased with liquid rate. The data from absorption measurements were evaluated with predictions based upon plug-flow and axial dispersion model. Mass transfer coefficients were found greater in case of axial dispersion model than that of plug-flow model specially at low Reynolds number (Re₁ < 1).Hydrogenation of α-methylstyrene to cumene using a Pd/Al₂O₃ catalyst was taken as a model reaction. Intrinsic kinetic studies were made in a laboratory-stirred-autoclave. Mass transfer coefficients were determined using these intrinsic kinetic data from the process kinetic measurements in trickle-bed reactor. Mass transfer coefficients under reaction conditions were found to be considerably higher than those obtained by absorption measurements.Correlations were suggested for predicting mass transfer coefficients at low Reynolds number.The gas to liquid mass transfer coefficients for lower gas and liquid flow rates were determined in a laboratory trickle-bed reactor. The effect of axial dispersion on mass transfer was considered in order to evaluate the experimental data. Three correlations were formulated to calculate the mass transfer coefficients, which included the effect of liquid loading, particle size and the properties of the reacting substances. The gas flow rate influences the gas to liquid mass transfer only in the region of low gas velocities. In the additional investigations of gas to liquid mass transfer without reaction in trickle-bed reactor, the mass transfer coefficients were determined under reaction conditions and the intrinsic kinetics was studied in a laboratory scale stirred autoclave with suspended catalyst. A few correlations are formulated for the mass transfer coefficients. A comparison with the gas-liquid mass transfer coefficient obtained by absorption measurements showed considerable deviations, which were illustrated phenomenologically.     

Competitative adsorption of two dissolved organics onto activated carbon—II: Adsorption kinetics in batch reactors

Bi-solute adsorption of dissolved organics by activated carbon was studied in a finite bath system. The batch tests with strongly adsorbable species show that at low concentrations (X < 0.1 mmol/1) only external mass transfer resistance is rate-determining. For higher concentrations internal mass transfer becomes increasingly important. This behavior indicates that the diffusional process within the particle occurs predominantly in the adsorbed phase.Bi-solute calculations were performed, using only single-solute data. Systems with differing equilibrium behavior, but similar diffusive properties of both solutes, were described adequately by a model which takes into account diffusion in the liquid-filled pores and in the adsorbed phase, as well as external mass transfer. Deviations between measured and predicted rates can be observed for systems with large differences in the mobility of the diffusing molecules, or if counter diffusion inside the particles occurs. It is likely that the discrepancies in these cases are caused by diffusional interactions between the two different species in the adsorbed phase.     

Pretreatment and physical activation of acetylene cokes

Pretreatment of acetylene cokes at 450 °C with a mixture of nitrogen, oxygen and water vapour creates a relatively large surface area and some initial microporosity, further developed by water activation at 800 °C. For the same degree of burn-off, but without pretreatment, large micropores (L > 2–3 nm) are obtained and the external surface area remains small.     

Modification of CaCO3 precipitation rates by water-soluble nacre proteins

Mineral growth in nacre and other CaCO₃-containing biominerals is controlled by biopolymers. Water-soluble proteins were extracted from nacre of the sea snail Haliotis laevigata by dissolving the mineral phase with 6% acetic acid. The influence of this protein mixture on CaCO₃ precipitation rates was investigated at different concentrations. A well-established assay for measuring the pH-value during CaCO₃ precipitation with and without protein additives was extended by calculating maximum precipitation rates from the pH-values. It could be shown that precipitation rates are greatly influenced by the mixtures of water-soluble nacre proteins. At very low protein concentrations (0.02 μg/ml) a rate enhancement in comparison to the pure supersaturated calcium carbonate solution by a factor of 1.4 was observed. At higher protein concentrations, a strong inhibitory effect occurred, with total inhibition at concentrations of 1.0 μg/ml and higher. Two unspecific proteins (bovine serum albumin and lysozyme) showed little or no modification of precipitation rates. In vivo, the function of the strong inhibition of CaCO₃ precipitation by nacre proteins at higher concentrations is presumably to prevent uncontrolled crystallization in the extrapallial fluid. The rate-enhancing capability of proteins at low concentrations may be explained by the presence of acidic and/or hydrophilic moieties.