Solubility of astaxanthin in supercritical carbon dioxide

The solubility of astaxanthin in carbon dioxide was measured under supercritical conditions of a pressure range from 80 to 300 bar, and temperature range from 303 to 333 K, by using a dynamic flow-type. The solubility of astaxanthin increasing from 0.42×10⁻⁵ to 4.89×10⁻⁵ with higher temperature and pressure maintains certain density of supercritical carbon dioxide. The solubility data obtained were applied to the Chrastil model, based on the density of carbon dioxide. The data fitted well with the Chrastil model at most experimental conditions.     

Peroxidase-catalyzed polymerization ofp-cresol in supercritical CO2

The feasibility of the catalysis of horseradish peroxidase (HRP) in supercriticalCO ₂ was studied for the polymerization ofp-cresol in the presence of H₂O₂. The reactions were performed at 40‡C and 74.8 aim (1 100 psia) above the critical conditions ofCO ₂. In the initial tests with 2 mM ofP-crcsol and 1 mM of H₂O₂, more oligomers ofp-cresol were produced as more HRP was added. This indicates that HRP is active in supercritical CO₂. HRP was not completely inhibited by H₂O₂ at concentrations up to 20 mM. Increasing the initial concentrations ofp-cresol and H₂O₂ to 20 mM, respectively, resulted in the formation of precipitates which were undissolved either in water or in dimcthylforamide (DMF). The effects of adding water and/or methanol as cosolvents on the reactivity of HRP were studied subsequently. When more than 13.3 mL of water per liter of reaction volume was added, the formation of precipitates was not observed. The reactivity of HRP was sustained when up to 11.8 mL of methanol per liter of reaction volume was added. In most cases conversion ofP-cresol was less than 50% for 5 hours of reaction time.     

Mass transfer enhancement in supercritical fluid extraction by acoustic waves

A computational fluid dynamics model of extraction of a solute (caffeine) from a porous solid matrix (coffee beans) using a supercritical solvent (carbon dioxide) is developed. Supercritical fluid extraction of a solute from a solid matrix is a slow process even when solute free solvent is circulated. The use of acoustic waves represents a potential efficient way of enhancing mass transfer processes. The effect of acoustically excited flows on supercritical fluid extraction from a porous solid matrix is investigated. The mathematical model considers diffusion-controlled regime in the porous solid matrix and convective-diffusive transport in the bulk fluid. Henry's law is used to describe the equilibrium states of the solid and the fluid phases. Accurate representation of the thermo-physical properties of supercritical solvent is considered by using the NIST Standard Reference Database 12. The conservation equations for mass, momentum, energy and species are numerically solved using implicit finite volume method. The effect of process parameters, such as initial state (pressure and temperature) of solvent and acoustic waves on the yield of solute extraction is also investigated numerically.     

Mathematical modeling of heat and mass transfer in hot gas spray systems

A mathematical model is developed to study simultaneous heat and mass transfer in hot gas spray systems. The model is obtained by writing mass, energy, and momentum balances for both continuous and discontinuous phases. Governing equations along with suitable correlations for heat and mass transfer coefficients have been solved numerically. In order to develop a realistic model for such complicated systems, a droplet size distribution was implemented in the model instead of using an average size. A steady state spray-cooling problem is analyzed to illustrate the applicability of the model. To validate the mathematical model for this case, necessary data was collected and measured in commercial cement plants. A good agreement between plant data and the model was noticed in general, and results obtained from the model indicate that size distribution of water droplets and physical dimensions of the spray-cooling system are important parameters. This model is very useful in determining the so-called "critical operation condition" at which sludge formation at the bottom of spray-cooling systems will happen. The predicted parameters in spray-cooling systems both for droplet phase and gas phase aptly illustrate the ability of the model to treat the complex phenomena associated with two-phase flows.     

Frequency response of microcantilevers immersed in gaseous,liquid, and supercritical carbon dioxide

The frequency response of ferromagnetic nickel microcantilevers with lengths ranging between 200 μm and 400 μm immersed in gaseous, liquid and supercritical carbon dioxide (CO₂) was investigated. The resonant frequency and the quality factor of the cantilever oscillations in CO₂ were measured for each cantilever length in the temperature range between 298 K and 323 K and the pressure range between 0.1 MPa and 20.7 MPa. At a constant temperature, both the resonant frequency and the quality factor were found to decrease with increasing pressure as a result of the increasing CO₂ density and viscosity. Very good agreement was found between the measured cantilever resonant frequencies and predictions of a model based on simplified hydrodynamic function of a cantilever oscillating harmonically in a viscous fluid valid for Reynolds numbers in the range of [1;1000] (average deviation of 2.40%). At high pressures of CO₂, the experimental Q-factors agreed well with the predicted ones. At low CO₂ pressures, additional internal mechanisms of the cantilever oscillation damping caused lowering of the measured Q-factor with respect to the hydrodynamic model predictions.     

Measurement and modeling solubility of bioactive coumarin and its derivatives in supercritical carbon dioxide

To design a supercritical fluid extraction process for the separation of bioactive substances from natural products, a quantitative knowledge of phase equilibria between target biosolutes and solvent is necessary. How-ever, mostly no such information is available in literature to date. Thus in the present study, illustratively the solubility of bioactive coumarin and its various derivatives (i.e., hydroxy-, methyl-, and methoxy-derivatives) in supercritical CO₂ were measured at 308.15–328.15 K and 10–30 MPa. Also, the pure physical properties such as normal boiling point, critical constants, acentric factor, molar volume and standard vapor pressure for coumarin and its derivatives were estimated. By these estimated information, the measured solubilities were quantitatively correlated by an approximate lattice equation of state proposed recently by the present authors.     

Kinetics and rate of enzymatic hydrolysis of cellulose in supercritical carbon dioxide

Experiments were carried out on the application of supercritical fluid to the hydrolysis of cellulose by the enzyme, cellulase. The stability of cellulase was sustained at the pressures of up to 160 atm for 90 min at 50 ‡C in supercritical carbon dioxide. In the hydrolysis of cellulose the glucose yield was 100% at supercritical condition. Kinetic constants of hydrolysis at supercritical condition were increased as compared to those at atmospheric condition. The hydrolysis reaction was found competitively inhibited by glucose at supercritical condition.     

Artificial Neural Networks Modeling of Ozone Bubble Columns: Mass Transfer Coefficient,Gas Hold-Up,and Bubble Size

This study aims at applying artificial neural network (ANN) modeling approach in designing ozone bubble columns. Three multi-layer perceptron (MLP) ANN models were developed to predict the overall mass transfer coefficient (k_La, s^?1), the gas hold-up (? _G , dimensionless), and the Sauter mean bubble diameter (d_S , m) in different ozone bubble columns using simple inputs such as bubble column's geometry and operating conditions. The obtained results showed excellent prediction of k_La, ? _G , and d_S values as the coefficient of multiple determination (R² ) values for all ANN models exceeded 0.98. The ANN models were then used to determine the local mass transfer coefficient (k_L , m.s^?1). A very good agreement between the modeled and the measured k_L values was observed (R² ?=?0.85).     

Dye solubility in supercritical carbon dioxide. Effect of hydrogen bonding with cosolvents

The use of supercritical carbon dioxide is emerging as a potential method for achieving pollution-free dyeing. An important factor in supercritical fluid dyeing is the solubility of the dye in supercritical carbon dioxide. Our measurements show that the solubility of C. I. Disperse Red-60 dye in supercritical carbon dioxide is significantly enhanced upon addition of polar csolvents : ethanol and acetone. The solubility enhancement is attributed to the formation of hydrogen bonds between cosolvent and dye molecules. Observed solubility behavior is correlated using dilute-solution theory with lattice-fluid-hydrogen-bonding model. Needed physical and hydrogen-bonding molecular parameters are estimated using the experimental data.     

Mass transfer coefficients in a pulsed packed extraction column

The volumetric overall mass transfer coefficients have been measured in a pulsed packed extraction column using diffusion model for the toluene/acetone/water system. The experiments were carried out for both mass transfer directions. The effects of operational variables such as pulsation intensity and dispersed and continuous phases flow rates on volumetric overall mass transfer coefficients have been investigated. The experimental findings indicate that pulsation intensity and mass transfer direction have great influence on volumetric overall mass transfer coefficient. Significant, but weaker, are the effects of continuous and dispersed phase flow rates. The experimental results obtained in the present work are compared with some other types of extraction columns. Finally, two empirical correlations for prediction of the continuous phase overall mass transfer coefficient is derived in terms of Sherwood and Reynolds numbers. Good agreement between prediction and experiments was found for all operating conditions that were investigated.     

Density correlation of solubility of C. I. disperse orange 30 dye in supercritical carbon dioxide

The solubility of C. I. Disperse Orange 30 (O30) dye in CO₂ has been measured by using a closed-loop (batch) solid-fluid equilibrium apparatus at temperatures between 313 and 393 K and at pressures between 11 and 33 MPa. Kumar and Johnston’s equation based on Chrastil’s concept has been used to describe the experimental solubility data. The solubility versus density plot appears much simpler than the solubility versus pressure plot. The isotherms are nearly straight and parallel to each other, as seen in the previous studies. Peng-Robinson equation of state (PR EOS) has also been used successfully in modeling the dye solubility in supercritical carbon dioxide as a function of pressure or density of the fluid phase. The validity of this method has been verified by the vapor pressure calculation. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Mathematical modeling of penicillin G Extraction by a bifunctional surfactant in a continuous extraction column

A bifunctional surfactant was used as a carrier of penicillin G for its continuous extraction by an emulsion liquid membrane without an extradant in a countercurrent extraction column of Oldshue-Rushton type. A permeation model was presented to describe transport mechanism of penicillin G in the continuous extraction system, including an axial dispersion model for the continuous phase and a mass transfer model for the dispersed emulsion phase. The mass transfer model describes the external mass transfer around the emulsion drop, the reaction at the external interface, the diffusion as well as the reaction equilibrium within the w/o emulsion drop, and the pH change of internal aqueous phase. Here, we considered three experimental variables: penicillin G concentration, pH of continuous phase and surfactant concentration. The calculated results from the permeation model fitted the experimental data well. This paper is dedicated to Dr. Youn Yong Lee on the occasion of his retirement from Korea Institute of Science and Technology.     

Gas-liquid mass transfer in a slurry bubble column operated at gas hydrate forming conditions

Gas-liquid interphase mass transfer was investigated in a slurry bubble column under CO₂ hydrate forming operating conditions. Modeling gas hydrate formation requires knowledge of mass transfer and the hydrodynamics of the system. The pressure was varied from 0.1 to 4 MPa and the temperature from ambient to 277 K while the superficial gas velocity reached 0.20 m/s. Wettable ion-exchange resin particles were used to simulate the CO₂ hydrate physical properties affecting the system hydrodynamics. The slurry concentration was varied up to 10%vol. The volumetric mass transfer coefficient (k_la_l) followed the trend in gas holdup which rises with increasing superficial gas velocity and pressure. However, k_la_l and gas holdup both decreased with decreasing temperature, with the former being more sensitive. The effect of solid concentration on k_la_l and gas holdup was insignificant in the experimental range studied. Both hydrodynamic and transport data were compared to best available correlations.     

Reactive extraction of lactic acid in a packed column

Reactive extraction of lactic acid was performed continuously in a packed column. The 0.6 M trioctylamine (TOA)/l-chlorobutane system was used as an extradant. The initial concentration of lactic acid was 10 wt% based on fermentation results. Raschig rings (5 and 7 mm diameter) were used to measure hydrodynamic data. Disperse phase holdup was nearly constant at V_d<0.8V_d,f.It can be seen that the flooding data obtained from this study were consistent with the literature. NTU and HTU were calculated. NTU varied from 1 to 2 and HTU from 96 cm to 44 cm with variation of V_d. The overall mass transfer coefficients of the continuous phase were nearly constant to 8.98x 10^-5 mol/cm²s with variation of V_d.     

Mass transfer and deodorization efficiency in a countercurrent spray tower for low superficial gas velocities

The aim of this study was to characterize mass transfer and deodorization efficiency in a countercurrent spray tower for low superficial gas velocities. The influence of operating parameters (U_G = 0.005 to 0.025 m s^?1, U_L = 6.1 × 10^?5 to 2.4 × 10^?4 m s^?1) on the liquid retention (ε_L), the drop diameter (d_g), the interfacial area (a) and the overall liquid and gas phase mass transfer coefficients (K_La, K_Ga) were estimated. The spray efficiency of some malodorous compounds was also estimated. A negative influence of the superficial gas velocity was demonstrated, during the spraying of water or chemical neutralizing scrubbing solutions. There was also an increase with the liquid flow rate. Abatements obtained were very good with respect to ammonia (>90%), and acceptable for the other compounds.     

Mass transfer of carbon dioxide in aqueous polyacrylamide solution with methyldiethanolamine

Carbon dioxide was absorbed into aqueous polyacrylamide (PAA) solution containing methyl-diethanolamine (MDEA) in a flat-stirred vessel to investigate the effect of non-Newtonian rheological behavior of PAA on the rate of chemical absorption of CO₂, where the reaction between CO₂ and MDEA was assumed to be a first-order reaction with respect to the molar concentration of CO₂ and MDEA, respectively. The liquid-side mass transfer coefficient (k_L), which was obtained from the dimensionless empirical equation containing the viscoelasticity properties of a non-Newtonian liquid, was used to estimate the enhancement factor due to chemical reaction. PAA with elastic property of non-Newtonian liquid made the rate of chemical absorption of CO₂ accelerate compared with a Newtonian liquid     

Effect of pressure fluctuations on the heat transfer characteristics in a pressurized slurry bubble column

The hydrodynamics and heat transfer characteristics were investigated in a slurry bubble column reactor whose diameter was 0.0508 m (ID) and 1.5 m in height. Effects of gas velocity (0.025–0.1 m/s), pressure (0.1–0.7MPa), solid concentration (0–20 vol%) and liquid viscosity (1.0–38.0 mPa s) on the hydrodynamics and heat transfer characteristics were examined. The pressure difference fluctuations were analyzed by means of attractor trajectories and correlation dimension to characterize the hydrodynamic behavior in the column. The gas holdup increased with increasing gas velocity or pressure, but decreased with increasing solid concentration or liquid viscosity. It was found that the attractor trajectories and correlation dimension of pressure fluctuations were effective tools to describe the hydrodynamic behaviors in the slurry bubble column. The heat transfer coefficient increased with increasing pressure or gas velocity, but decreased with increasing solid concentration or viscosity of slurry phase in the slurry bubble column. The heat transfer coefficient value was well correlated in terms of operating variables and correlation dimension of pressure fluctuations in the slurry bubble column.     

Phase behavior of water-insoluble simvastatin drug in supercritical mixtures of chlorodifluoromethane and carbon dioxide

Phase behavior data are presented for simvastatin, a water-insoluble drug, in supercritical solvent mixtures of chlorodifluoromethane (CHClF₂) and carbon dioxide (CO₂). The solubilities of the simvastatin drug in the solvent mixtures of CHClF₂ and CO₂ were determined by measuring the cloud point pressures using a variable-volume view cell apparatus as functions of temperature, solvent composition, and amount of the drug loaded into the solution. The cloud point pressure increased with increasing the system temperature. As the CHClF₂ composition in the solvent mixture increased, the cloud point pressure at a fixed temperature decreased. Addition of CHClF₂ to CO₂ caused an increase of the dissolving power of the mixed solvent for the simvastatin drug due to the increase of the solvent polarity. CHClF₂ acted as a solvent for simvastatin, while CO₂ acted as an anti-solvent. The cloud point pressure increased as the amount of the simvastatin drug in the solvent mixture increased. Consequently, the solubility of the simvastatin drug in the solvent mixture of CHClF₂ and CO₂ decreased with increasing the CO₂ content in the solvent mixture as well as with increasing the system temperature.     

Heat transfer in a liquid-liquid spray column

A theoretical and experimental study of direct contact heat transfer in a kerosene-water spray column has been carried out. A mathematical model for the process with a drop size distribution is proposed, and the associated computer program for the numerical solution developed. Correlations for the overall area heat transfer and axial dispersion coefficients for the column were obtained. Applying the mathematical model with experimentally obtained parameters, temperature profiles of both phases could be predicted. Comparisons with previous work in the literature support the present study. From the results, operation with uniform drop size in a short column is recommended.