Mass transfer coefficients of styrene and oxygen into silicone oil emulsions in a bubble reactor

The absorption of oxygen and styrene in water-silicone oil emulsions was independently studied in laboratory-scale bubble reactors at a constant gas flow rate for the whole range of emulsion compositions (0-10% v/v). The volumetric mass transfer coefficients to the emulsions were experimentally measured using a dynamic absorption method. It was assumed that the gas phase contacts preferentially the water phase. In the case of oxygen absorption, it was found that the addition of silicone oil hinders oxygen mass transfer compared to an air-water system. Decreases in k_La_oxygen of up to 25% were noted. Such decreases in the oxygen mass transfer coefficient, which imply longer aeration times to transfer oxygen, could represent a limiting step in biotechnological processes strongly dependent on oxygen concentration. Nevertheless, as the large affinity of silicone oil for oxygen enables greater amounts of oxygen to be transferred from the gas phase, it appears that the addition of more than 5% silicone oil should be beneficial to increase the oxygen transfer rate. In the case of styrene absorption, it was established that the volumetric mass transfer coefficient based on the emulsion volume is roughly constant with the increase in the emulsion composition. In spite of the relatively high cost of silicone oil, water-silicone oil emulsions remain relevant to treat low-solubility volatile organic compounds, such as styrene, in low-concentration gas streams.     

The role of diffusional resistance on crystal growth: Interpretation of dissolution and growth rate data

Experimental results on crystal growth and dissolutions kinetics were taken from literature to test two theoretical models describing the crystal growth from solutions. One of the models, designated by two-step model (TSM), is being used for many years to describe the relation between crystal growth rates with supersaturation, temperature and hydrodynamic conditions. The other model was presented in a previous work and will be called concurrent-step model (CSM). The chosen literature data allowed calculating the mass transfer coefficients during crystal growth, for different hydrodynamic conditions. The obtained results are interpreted taking into consideration well-established mass transfer theories. According to the TSM, the measured crystal growth kinetics can only be explained by means of an unrealistic variation of the mass transfer coefficient with the relative crystal-solution velocity. Conversely, mass transfer coefficients obtained by the CSM were confirmed by appropriate semi-theoretical correlations, both in their order of magnitude and in their behaviour. In addition, crystal growth and dissolution experiments of sucrose were carried out at in a batch crystallizer for different agitation speeds. The resulting kinetics are used to test the CSM in a system that is significantly different from the inorganic salts used in the analysed literature works. As predicted by this model, the existence of an adsorbed layer in the crystal surrounding is likely to have affected the solute molecular diffusivity in the medium. Based on this premise, the results obtained with sucrose are well described by the CSM.     

Improvement of oxygen mass transfer estimation from oxygen concentration measurements in bubble column reactors

An original procedure has been established for estimating the overall volumetric mass transfer coefficient using the oxygen concentration curves resulting from the usual gassing-in and gassing-out method. This procedure was applied to experimental data obtained in a small scale bubble column using both tap water and a coalescence-inhibiting liquid mixture that represents the coalescence behavior of biological media. It is based on the analysis of the characteristics times of the system, including those of the hydrodynamics of the two phases, the sensor dynamics and the system inertia when the gas composition is modified. A numerical procedure was developed to estimate the characteristic time of the system inertia t_i, using the assumption that this inertia is nearly independent of superficial gas velocity U_G. The calculations confirmed that the optimized t_i value was nearly independent of U_G and of the coalescence behavior of the liquid phase. Additionally, the resulting K_La_L values for tap water were closer to the correlation of Shah et al. [1982. Design parameters estimations for bubble column reactors. A.I.Ch.E. Journal 28, 353-379] than those of other conventional models. Finally, the original procedure was also reported to reduce significantly the square sum deviation between the predicted and the measured oxygen response curves.     

The hydrogenation of cinnamaldehyde by supported aqueous phase (SAP) catalyst of RhCl(TPPTS)3: Selectivity, kinetic and mass transfer aspects

The hydrogenation of trans-cinnamaldehyde catalysed by a supported aqueous phase catalyst of RhCl(TPPTS)₃ [TPPTS: trisodium salt of tris(m-sulfophenyl)phosphine] on silica was investigated in terms of the product selectivity, reaction kinetics and mass transfer characteristics. The hydrogenation is selective at the CC bonds in cinnamaldehyde giving hydrocinnamaldehyde as the main product. To achieve high selectivity (99.9%), it is necessary to employ a low initial concentration of cinnamaldehyde (0.076 M). The selectivity also depended on the reaction operating conditions (pressure, temperature, catalyst loading) and the water content property of the SAP catalyst. Optimum water content of the SAP catalyst giving maximum activity was obtained when the pore volume of the supports was completely filled with water. The overall order of reaction was first-order and therefore the conventional three-phase slurry model was applied to the SAP system for the mass transfer analysis. The gas-liquid mass transfer and the reaction resistances were the controlling steps of comparable significance, while liquid-solid mass transfer resistance was negligible in this system. Under similar conditions, the SAP catalyst gave a lower reaction rate than the analogous biphasic catalyst.     

Vapour- and liquid-side volumetric mass transfer coefficients measured in distillation column. Comparison with data calculated from absorption correlations

Volumetric mass transfer coefficients in liquid and vapour phases in distillation column were measured by the method consisting of a fitting of the concentration profile of liquid phase along the column obtained by the integration of a differential model to the experimental one. The mathematical model of distillation process includes mass and energy balances and the heat and mass transfer equations. The film model flux expressions with the convective transport contributions have been considered in the transfer equations. Vapour and liquid phases are supposed to be at their saturated temperatures along the column. Effect of changes of phase flows and physical properties of phases on the mass transfer coefficients along the column and non-ideal thermodynamic behaviour of the liquid phase have been taken into account. The concentration profiles of liquid phase are measured in the binary distillation of the ethanol-water and methanol-ethanol systems at total reflux on metal Pall Rings and Intalox saddles 25 mm in the column with diameter of 150 mm. The distillation mass transfer coefficients obtained by the fitting procedure are compared with those calculated from absorption data using Onda's, Billet's and Linek's correlations. The distillation heat transfer coefficients calculated from the model assuming saturated temperatures in both phases are compared with those calculated from the Chilton-Colburn and penetration model analogy between mass and heat transfer. The results have confirmed an agreement neither between distillation and from absorption correlations calculated mass transfer coefficients nor between analogy and from enthalpy balance calculated heat transfer coefficients. Also the concentration profiles obtained by the integration of the differential model of the distillation column using the coefficients from absorption correlation have differed from the experimental profiles considerably.     

The role of under-rib convection in mass transport of methanol through the serpentine flow field and its neighboring porous layer in a DMFC

Numerical simulation of a direct methanol fuel cell (DMFC) operating under discharging conditions is challenged by the difficulties in modeling of complicated liquid-gas two-phase flows and coupled electrochemical kinetics. Under open-circuit conditions, the net electrochemical reactions in the DMFC anode cease, but, owing to the methanol concentration difference between the anode and cathode, the mass transport of methanol remains, creating a mass transport process of methanol in a single-phase liquid flow with no electrochemical reactions in the DMFC anode. Consequently, an accurate simulation of mass transport of methanol under such open-circuit conditions becomes possible. In this work, we performed a 3D numerical simulation of mass transport of methanol in the DMFC anode under open-circuit conditions and obtained the mass flux of methanol through the porous layer for different values of permeability. We also measured the mass flux of methanol permeation from the anode flow field to the cathode under open-circuit conditions. The comparison between the numerical and measured mass flux of methanol made it possible to in situ determine the permeability of the typical commercial porous layer. Using this in situ determined permeability, we then investigated numerically the effect of methanol feed rates on mass transport and found that the in-plane under-rib convection plays an important role, even at low methanol feed rate, to make the reactant evenly distributed over the entire catalyst layer.     

Oryctes monoceros Trapping with Synthetic Pheromone and Palm Material in Ivory Coast

Oryctes monoceros is the most serious pest in coconut plantations, causing up to 40% damage in tropical Africa, especially in Ivory Coast. With a view to reducing pest populations by olfactory trapping, field trials were carried out to assess the efficiency of a synthetic aggregation pheromone: ethyl 4-methyloctanoate (1), 4-methyloctanoic acid (2), a related volatile produced by males, and decaying palm material, either oil palm empty fruit bunches (EFB) or pieces of coconut wood (CW) of various ages. Vertical polyvinyl chloride tube traps (2 × 0.16 m with two openings in the upper half), embedded in the soil, were more efficient than 30-L pail traps 1.5 m above ground. EFB, which were inactive alone, synergized captures with synthetic pheromone. CW was more effective than EFB in comparative trials. Compound 2 did not catch any beetles when assessed with EFB, and reduced catches by 1 + EFB when tested at >10% with the pheromone. Trapping over 6 mo in 2002 and 2003 in a 19-ha coconut plot inside a 4,000-ha oil palm estate reduced damage from 3.8% in 2001 to 0.5% in 2002, then to 0.2% in 2003. Damage was 0.0% in 2004 with routine trapping using 32 traps, which caught 3369 beetles in 9 mo. The results are discussed in relation to other Dynastid palm pests and coconut protection in Ivory Coast.     

Fractionation of pitches by molecular weight using continuous and semibatch dense-gas extraction

A countercurrent, multistage, dense-gas extraction technique with reflux was investigated for the fractionation of carbonaceous pitches. Two modes of operation were investigated: continuous-stripping and semibatch operation. For example, continuous stripping with dense-gas toluene in the supercritical state, a positive column temperature gradient from 330 to 380 °C, and a pressure of 49 bar was used to strip the monomer and dimer species from an A-240 petroleum pitch feed, yielding a high molecular weight (mol wt) bottoms product rich in trimer and higher oligomers. Afterwards, semibatch operation was used with supercritical, dense-gas toluene, a temperature gradient of 330 to 380 °C, and pressures from 84 to 111 bar to fractionate the above bottoms product, yielding a trimer-rich overhead (average mol wt (M_w) = 800) and a tetramer and higher residue with M_w ∼ 1000. Considering the two operations as a unit, a combined selectivity factor of ∼350 was obtained. Not only is this at least an order of magnitude better than what can in principle be accomplished by conventional, single-stage solvent extraction, but such extraction is inapplicable to our system because of the insolubility of the pitch fractions of interest in typical liquid solvents. Matrix-assisted, laser desorption/ionization time-of-flight mass spectrometry (MALDI) was used to verify that separation was indeed occurring by mol wt and to study the relationship between the M_w, softening point, and C/H ratio of the fractions produced.     

Mass transfer to clean bubbles at low turbulent energy dissipation

Experimental gas-liquid mass transfer data from a system where single bubbles are kept stationary by a low turbulence downward liquid flow are compared with predictions from theoretical models which take turbulence into account. The data clearly show that, for the turbulence intensities at play, turbulence does not affect mass transfer. Higbie's equation with contact time t_e=d/u may be used for the calculation of the gas-liquid mass transfer coefficient of clean bubbles in systems with levels of turbulent kinetic energy dissipation of, at least, up to .     

The effect of ionic liquids on product yield and catalyst stability

The effect of ionic liquids on product yield and catalyst stability has been investigated through Suzuki cross-coupling of phenylboronic acid and 4-bromoacetophenone in organic solvents, ionic liquids and mixtures of organic solvents and ionic liquids.