Mass and heat transfer analysis of SAS: effects of thermodynamic states and flow rates on droplet size

The supercritical antisolvent (SAS) process entails attainment of extremely high supersaturation in an atomized solution droplet by a very rapid increase in the antisolvent CO₂ mole fraction in it during its flight through a CO₂ continuum. In this work the droplet dynamics has been studied for a single droplet of CO₂–acetone solution falling in a flowing CO₂ environment in terms of variations in its concentration, temperature and size due to the two-way mass transfer of CO₂ and solvent. A model based on the SAS mechanism of simultaneous mass and heat transfer has been simulated to study the effects of the thermodynamic states and the individual flow rates of CO₂ and solution. The hydrodynamics of the droplet and the convective mass and heat transfer have been combined in the model to ascertain the individual number of moles of CO₂ and solvent transferred and their directions at any instant of time during the flight. The effects of process parameters have been analyzed for the initial droplet size of the solution. The swelling or shrinking of the droplet has been analyzed with time till the solvent is completely evaporated, in the pressure range of 71–350 bar, temperature range of 313–333 K, SC CO₂ flow rate of 0.1136–1.136 mol/s and the ratio of the volumetric flow rates of CO₂-to-solution in the range of 100–1000. The mole fraction of CO₂ attained inside the non-isothermal droplet has been analyzed with time, which is needed in the design of supersaturaton and nucleation kinetics in the SAS process.     

Modeling of precipitation of ultra-fine particles by pressure reduction over CO2-expanded liquids

A mathematical model has been developed to describe the process of precipitation of ultrafine particles by pressure reduction over gas (CO₂)-expanded liquids. A rapid pressure reduction over a CO₂-expanded organic solution, from 30–70 to 1 bar at 303 K decreases the solution temperature by 30–80 K in a very short span of time (0.5–1.5 min), which generates a rapid, high, and uniform supersaturation of the dissolved solute in the solution and facilitates precipitation of ultrafine particles. The model developed in this work estimates the supersaturation attained, nucleation and growth rates obtained during the pressure reduction over CO₂-expanded organic solutions, and the particle size distribution of the precipitated particles. Cholesterol has been chosen as a model solute to be precipitated, and acetone has been chosen as a solvent. A new method has been developed for prediction of equilibrium solubility of solute which is affected by a decrease in CO₂ mole fraction as well as a simultaneous decrease in solution temperature during pressure reduction. This method combines the semi-empirical approach of using the partial molar volume fraction of solvent in a CO₂-solvent binary mixture and solid–liquid equilibrium data for a solute–solvent system. Size distributions of the precipitated particles have been calculated assuming primary nucleation (homogeneous as well as heterogeneous nucleation) and diffusion-limited growth kinetics. The predicted mean average particle sizes are then compared with the size of cholesterol particles precipitated by pressure reduction of a CO₂-expanded acetone solution of cholesterol. The particle sizes predicted assuming heterogeneous nucleation are found to be closer to the experimentally observed particle sizes, indicating that the heterogeneous nucleation could be the main mechanism of nucleation, which could occur at the gas–liquid interface of the CO₂ bubbling out of CO₂-expanded solution during pressure reduction.     

Parameters controlling supersaturation by DELOS using carbon dioxide

The present work pertains to estimation of the maximum degree of supersaturation that can be attained in an organic solution by the DELOS process using carbon dioxide (CO₂) as a cosolvent. The paper analyzes the effects of initial mole fraction of carbon dioxide, temperature and pressure on the degree of supersaturation of cholesterol in a CO₂—acetone—cholesterol solution. It has been observed that owing to liberation of large amounts of CO₂ very large temperature drops may be attained by depressurization, resulting in attainment of very high supersaturation. Within the ranges of the parameters studied in this work, the degree of supersaturation is higher with higher values of initial temperature and initial CO₂ mole fraction of the solution due to inverse interdependence of the final temperature and the residual CO₂ mole fraction in the depressurized solution. Copyright © 2006 Society of Chemical Industry     

A novel equation of state (EOS) for prediction of solute solubility in supercritical carbon dioxide: Experimental determination and correlation

Solubility data of organophosphorous metal extractants in supercritical fluids (SCF) are crucial for designing metal extraction processes. We have developed a new equation of state (EOS) based on virial equation including an untypical parameter as BP/RT, reduced temperature and pressure for prediction of solute solubility in supercritical carbon dioxide (SC CO₂). Solubility experimental data (solubility of tributylphosphate in SC CO₂) were correlated with the two cubic equations of state (EOS) models, namely the Peng–Robinson EOS (PR‐EOS) and the Soave–Redlich–Kwong EOS (SRK‐EOS), together with two adjustable parameter van der Waals mixing and combining rules and our proposed EOS. The AARD of our EOS is significantly lower than that obtained from the other EOS models. The proposed EOS presented more accurate correlation for solubility data in SC CO₂. It can be employed to speed up the process of SCF applications in industry.     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

Effect of pressure and non-isothermal injection on re-crystallization by CO2 antisolvent: Solubility measurements,simulation of mixing and experiments

This work investigated for the first time a CO₂ antisolvent crystallization (SAS) operating in non-isothermal conditions, i.e. injection of a solution warmer than that of the CO₂ – in order to impose an additional driving for crystallization when CO₂ was not a strong antisolvent. The approach focused on phase equilibria (with a distinctive feature of being modeled by artificial neural network) and 3D-simulation of the mixing (considering both heat and mass transfers) in order to detail the supersaturation profiles in the mixing zone and confronted them to the crystallization results. The effect of pressure was investigated as well. The solubility of a model compound, mefenamic acid (MEFE) was measured in CO₂–acetone at 35 °C/8.5, 10 and 15 MPa, and 10 MPa/25, 35 and 45 °C and further correlated by a neural network to provide an easy-to-handle equation of MEFE concentration. Simulations results showed that supersaturation levels were low (around 2) and that the expanding jet spread similarly whatever the pressure. The effect of differential temperature on the mixing behavior and supersaturation was investigated. Compared to isothermal cases, higher superaturations were obtained but only if a more concentrated solution allowed by the higher temperature was processed as well. The benefit for the crystal size was difficult to evidence because of the long sizes of the needles and the difficulties of processing almost saturated solutions. Investigation of a less CO₂–acetone compound would be more promising.     

High-pressure phase equilibrium measurements and thermodynamic modeling for the systems involving CO2, ethyl esters (oleate,stearate, palmitate) and acetone

The aim of this work was to study the phase behavior of systems involving carbon dioxide (CO₂), fatty acid ethyl esters (ethyl oleate, ethyl stearate and ethyl palmitate) and acetone at high pressures. The phase behavior involving these components is an important step regarding the design and optimization of industrial processes based on supercritical conditions, such as biodiesel production and fatty esters fractionation involving supercritical and/or pressurized solvents. In addition, supercritical CO₂ can offer an interesting alternative for glycerol separation in water-free biodiesel purification processes. The binary systems investigated in this work were CO₂ + ethyl oleate, and CO₂ + ethyl stearate and these were compared with the CO₂ + ethyl palmitate system. The ternary CO₂ + ethyl palmitate + acetone was also investigated at two different ethyl palmitate to acetone molar ratios of (1:1) and (1:3). The static synthetic method using a variable-volume view cell was employed to obtain the experimental data in the temperature range of 303.15–353.15 K. Vapor–liquid (VL), liquid–liquid (LL) and vapor–liquid–liquid (VLL) phase transitions were observed in these systems. In the binary systems, the solubility increased with the presence of unsaturation and decreased with the number of carbon atoms in the fatty ester chain. Addition of acetone as well as ethanol eliminated the liquid–liquid immiscibility and reduced the pressure transitions, therefore increasing the solubility of the ester in supercritical CO₂. The experimental data sets for the binary and ternary systems were successfully modeled using the Peng–Robinson equation of state with the classical van der Waals quadratic mixing rule (PR-vdW2) and Wong-Sandler (PR-WS) mixing rule. Both models showed good performance in the phase equilibrium correlations and in predictions for the binary and ternary systems.     

Micronization and characterization of drug substances by RESS with supercritical CO2

A RESS (rapid expansion of supercritical solution) process for the preparation of ultra-fine drug particles with no organic solvent has been developed with supercritical CO₂. Three drug substances with different solubility in supercritical CO₂ were used, and orifice disks and capillary tubes were adapted as an expansion device. The solubilities of drug substances in supercritical CO₂ and the effects of various operating parameters on the characteristics of the particles prepared by RESS process were experimentally investigated. The solubility of the drug substance in supercritical CO₂ had a major effect on the average diameter of the particle prepared by RESS process, and the particle diameter decreased with the solubility for all the drugs and operating conditions. The particle diameter also decreased with preexpansion temperature and increased with the hole diameter of the orifice nozzle and aspect ratio (L/D) of the capillary tube.     

Supercritical CO2 extraction of Helichrysum italicum: Influence of CO2 density and moisture content of plant material

Kinetics and selectivity of supercritical carbon dioxide (SC CO₂) extraction of Helichrysum italicum flowers were analyzed at pressures in the range of 10-20 MPa and temperatures of 40 °C and 60 °C (density of SC CO₂ from 290 to 841 kg/m³) and also at 10 MPa and 40 °C using flowers with different moisture contents (10.5% and 28.4%). Increased moisture content of H. italicum flowers resulted in enchased solubility of solute enabling decrease of SC CO₂ consumption necessary for achieving desired extraction yield. The most abundant compounds in the supercritical extracts are sesquiterpenes and waxes while monoterpenes and sesquiterpenes are the main constituents of essential oil obtained by hydrodistillation. The optimal set of working parameters with respect to extraction yield, SC CO₂ consumption and chemical composition of extract were defined related to moisture content of raw material and SC CO₂ density.     

Controlled liquid antisolvent precipitation using a rapid mixing device

Particle formation by the liquid antisolvent (LAS) process involves two steps: mixing of solution–antisolvent streams to generate supersaturation and precipitation (which includes nucleation and growth by coagulation and condensation) of particles. Uniform mixing conditions ensure rapid and uniform supersaturation, making it a precipitation controlled process where the particle size is not further affected by mixing conditions and results in precipitation of ultra-fine particles with narrow particle size distribution (PSD). In this work, we demonstrate that the use of an ultrasonically driven T-shaped mixing device significantly improves mixing of solution and antisolvent streams for precipitation of ultra-fine particles in a continuous operation mode. LAS precipitation of ultra-fine particles of multiple active pharmaceutical ingredients (APIs) such as itraconazole (ITZ), ascorbyl palmitate (ASC), fenofibrate (FNB), griseofulvin (GF), and sulfamethoxazole (SFMZ) in the size range 0.1–30 μm has been carried out from their organic solutions in acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and ethanol (EtOH). Classical theory of homogeneous nucleation has been used to analyze the result, which suggests that higher nucleation rate results in finer particle size. Interestingly, experimental determination of degree of supersaturation indicates that higher supersaturation does not necessarily result in higher nucleation rate and nucleation rates can be correlated to solvent polarity.     

Growth of magnetic thin films using CO2 RESS expansions

A continuous-flow rapid expansion of supercritical solution (RESS) apparatus is used to grow thin iron oxide thin films under ambient and vacuum conditions. The magnetic thin films are produced by expanding a supercritical solution of ferric acetylacetonate (Fe(acac)₃) and CO₂ and directing the resulting supersonic jet onto both hot and cold silicon wafers. The concentration of the expanding solution is monitored in-line with a UV–vis high pressure view cell which is also used to perform solubility measurements. The resulting films contain nano- and sub-micronic particles in the 13–700 nm size range and show magnetic order. Structural and magnetic data for these thin particle films have been obtained by SQUID and SEM measurements and compared as a function of substrate surface temperature, growth times, and initial solute concentrations. Experimental and theoretical analysis of the thermodynamics and fluid mechanics appropriate for this RESS process is discussed.     

Prediction of solubilities of solid solutes in carbon dioxide-expanded organic solvents using the predictive Soave–Redlich–Kwong (PSRK) equation of state

In this study, the solubilities of solid solutes in carbon dioxide (CO₂)-expanded organic solvents are predicted using the predictive Soave–Redlich–Kwong (PSRK) equation of state (EOS). The liquid-phase compositions and volume expansion ratios of CO₂-expanded organic solvents are predicted prior to the solubility predictions. With predicted liquid-phase compositions and volumetric properties, the solubilities of cholesterol in CO₂-expanded acetone, naphthalene in CO₂-expanded toluene, stearic acid in CO₂ expanded ethyl acetate and tetradecanoic acid in CO₂-expanded ethyl acetate are predicted according to their reference solubilities in pure organic solvents. In addition to satisfactory predictions of liquid-phase composition and volume expansion ratios, the PSRK EOS also provides qualitative prediction ability for solubilities of solid solutes in CO₂-expanded organic solvent. This study demonstrated that the PSRK EOS was a simple model with predictive ability for solubility evaluation in preliminary process design and development for supercritical fluid technology using CO₂-expanded organic solvents.     

Activation of lipase by sol–gel coating with hydrophobic alkyl‐substituted silicates in supercritical carbon dioxide

BACKGROUND: Sol–gel entrapment of lipases is usually performed in an aqueous solution. A novel method of sol–gel coating of lipase in supercritical carbon dioxide (SC‐CO₂) is proposed. RESULTS: Crude lipase powder (Rhizopus oryzae) coated with hydrophobic silicates, derived from dimethyldimethoxysilane and tetramethoxysilane in SC‐CO₂ at 35 °C and 15 MPa, exhibited 5–7 times higher esterification activity than that prepared via an aqueous sol–gel route. Lipase immobilized in a methyl‐substituted silica monolith was also highly activated by sol–gel coating using the same silica precursors in SC‐CO₂. CONCLUSION: Sol– gel coating in SC‐CO₂, of lipases in powder and immobilized forms with hydrophobic alkyl‐substituted silicates provides an efficient tool for the enhancement of enzymatic activities in non‐aqueous media. Copyright © 2009 Society of Chemical Industry     

High‐pressure phase equilibria for a styrene/CO2/polystyrene ternary system

To reveal the possibility of supercritical (SC)‐CO₂‐assisted devolatilization of polystyrene, the equilibrium composition data for the CO₂ phase in a styrene/CO₂/polystyrene ternary system is determined by a semistatic experimental technique. The parameters in the lattice–fluid equation of state of Sanchez and Lacombe are determined for the investigated system. The distribution coefficients of styrene between the polymer and the supercritical fluid phases are investigated experimentally at 318 and 328 K over the pressure range of 12–20 MPa. The binary interaction parameter between styrene and CO₂ is obtained by regression of the vapor–liquid equilibrium data. The interaction parameter between CO₂ and polystyrene is calculated by using the sorption data from the literature, and the interaction parameter between styrene and polystyrene is optimized by using the measured data of this study. The investigation of the distribution coefficients indicates that styrene can be removed from polystyrene by SC‐CO₂ at near room temperature and moderately high pressures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1938–1944, 2002     

Styrene‐assisted free‐radical graft copolymerization of maleic anhydride onto polypropylene in supercritical carbon dioxide

The free‐radical graft copolymerization of maleic anhydride (MAH) onto polypropylene (PP) with the assistance of styrene (St) in supercritical carbon dioxide (CO₂) was studied. The effects of the St concentration and initiator concentration on the functionality degree of the grafted PP in supercritical CO₂ were investigated. The addition of St drastically increased the MAH functionality degree, which reached a maximum when the molar ratio of MAH and St was 1:1. St, an electron‐donating monomer, could interact with MAH through charge‐transfer complexes to form the St–MAH copolymer (SMA), which could then react with PP macroradicals to produce branches by termination between radicals. There was SMA in the grafting reaction system characterized by Fourier transform infrared and differential scanning calorimetry. Furthermore, the highest MAH functionality degree was obtained when the concentration of 2,2′‐azobisisobutyronitrile (AIBN) was 0.6 wt % based on PP. The effects of the temperature and pressure of supercritical CO₂ on the functionality degree of the grafted PP were analyzed. An increase in the temperature accelerated the decomposition rate constant of AIBN, thereby promoting the grafting reaction. In addition, an increase in the temperature increased the diffusion of monomers and radicals in the disperse reaction system of supercritical CO₂. The highest degree of functionality was found at 80°C. Also, the functionality degree of grafted PP decreased with an increase in the pressure of supercritical CO₂ within the experimental range. The morphologies of pure PP and grafted PP were significantly different under polarizing optical microscopy. The PP spherulites were about 38 μm in size, and the grafted PP spherulites were significantly reduced because of heterogeneous nucleation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 853–860, 2003     

High-pressure phase equilibria for the binary system carbon dioxide + dibenzofuran

The experimental solubility of dibenzofuran in near-critical and supercritical carbon dioxide and the solid–liquid–vapor (SLV) equilibrium line for the CO₂ + dibenzofuran system are reported. The built in-house static view cell apparatus used in these measurements is described. The solubility of naphthalene in supercritical CO₂ and the CO₂ + naphthalene SLV line are also determined in order to assess the reliability and accuracy of the measurement technique. The solubility of dibenzofuran in carbon dioxide is determined at 301.3, 309.0, 319.2, 328.7 and 338.2 K in the 6–30 MPa pressure range. Solubility data are correlated using the Chrastil model and the Peng–Robinson equation of state. This equation is also used to predict the CO₂ + dibenzofuran SLV line. Results show the feasibility of using supercritical CO₂ to extract dibenzofuran.     

Synthesis of single phase aragonite precipitated calcium carbonate in Ca(OH)2-Na2CO3-NaOH reaction system

The formation behavior of precipitated calcium carbonate polymorphs was investigated in three different supersaturation levels. Because the most easily adjustable and influential variable determining supersaturation is the ion concentration of the major reactants — Ca²⁺ and CO3 ₃ ²⁻ — the supersaturation can be adjusted by changing the ion concentration of these two ions. At high supersaturation, free energy is necessary for a decrease in nucleation, promoting the formation of a sphere-shaped vaterite, while aragonite and calcite were seen to co-exist at medium supersaturation. At low supersaturation, aragonite was mainly formed by mixing with some calcite. Hence, we considered that lower supersaturation was necessary to obtain a single phase aragonite. Furthermore, we found that the solubility of Ca(OH)₂ was decreased with the addition of NaOH by a common ion effect. Thus, it is possible to perform an experiment at a lower Ca²⁺ concentration. The aragonite was synthesized by adding the Na₂CO₃ solution to the Ca(OH)₂ slurry containing several concentrations of NaOH solution at 75°C and under the addition rate of Na₂CO₃ at 3 ml/min. The formation yield of calcite decreased when the NaOH concentration was increased. In conclusion, in the case of the reaction of the 2.5 M NaOH solution over 210 minutes, single-phase aragonite with an aspect ratio of 20 was obtained.     

A novel process for precipitation of ultra-fine particles using sub-critical CO2

Supercritical CO₂ has been utilized as solvent, cosolvent or antisolvent in several processes for production of ultra-fine solid particles with narrow size distribution. The key to the precipitation of such particles is to produce a very large, rapid and uniform supersaturation in the solution of a solid substance. This can be achieved either by a rapid and large reduction in the temperature of solution or by drastically increasing the CO₂ solubility for imparting the antisolvent effect. Most of these CO₂ processes require high-pressure pumps, specially designed nozzles and accurate control of process parameters. In order to obviate these requirements, a simple technique of precipitation by pressure reduction over the gas-expanded liquids (PPRGEL), such as CO₂-expanded organic solutions has been utilized to impart a large, uniform and rapid reduction of temperature in the solution for instantaneous precipitation of ultra-fine particles. This process utilizes sub-critical CO₂ at relatively low pressures of 40-70 bar and near ambient temperature of 303 K for creating a temperature drop of 30-70 K in the solution within seconds, without using any specially designed nozzle or high-pressure pumps. The present paper validates the process principle for precipitation of Zinc acetate (ZnAc) nanoparticles from its organic solution in a mixed solvent of acetone and dimethyl sulfoxide (DMSO). Nanoparticles are produced with the average size of 20-250 nm (from 100 ml of solution in a high-pressure vessel of 1.09 L working volume), and vary in shapes such as long needles, rods and near spherical depending on pressure (40-70 bar at 303 K), solid concentration (0.01-0.05 g/ml) and addition of stabilizer.     

Solubility of Na2SO4, Na2CO3 and their mixture in supercritical water

The solubility of many salts in water decreases dramatically with temperature in the vicinity of the critical point of pure water. Examples of these salts are sulfates of sodium, potassium, lithium and sodium carbonate. These salts are usually produced during supercritical water oxidation (SCWO) and contribute to fouling. The solubility of Na₂CO₃ and Na₂SO₄ has been determined in pure form and in the presence of each other, for the temperature range relevant to SCWO. The experimental procedure was to pass the salt solution through a tube at constant temperature. After a brief initiation period during which no salt sticks to the tube, the salt above the solubility limit deposited on the tube surface. The solution leaving the section was thus at the solubility limit. A rapid decrease in the salt solubility was observed just above the pseudo-critical temperature. For supercritical conditions, the solubility of each salt in the form of a mixture was quite close to the solubility of pure salt. At the highest fluid density considered (480 kg/m³) the presence of Na₂CO₃ reduces the solubility of Na₂SO₄, as might be expected from the “common-ion effect”.     

Effect of Stearic Acid as a Co‐solvent on the Solubility Enhancement of Aspirin in Supercritical CO2

The solubility of aspirin in supercritical CO₂ (SC‐CO₂) with stearic acid as a co‐solvent was measured at various pressures and temperatures. The experimental data were obtained by a static method. Stearic acid had a significant effect on the enhancement of solubility, as the aspirin solubility increased by up to 16 times. Further, the effect of stearic acid on the solubility enhancement of aspirin was compared with that of other co‐solvents. Different semi‐empirical models from the literature were applied for correlating the experimental data, proving good agreement with the experimental data. The model of Sung and Shim exhibited the lowest deviation from the obtained data. The results of the solubility test can be employed to produce aspirin‐based pharmaceuticals using supercritical fluid technology (SFT).