Partition Coefficients and Solubility of Urea-Fractionated Fatty Acid Ethyl Esters from Fish Oil in Supercritical CO2

Solubilities and K-values of urea-fractionated fish oil fatty acid ethyl esters, prepared from sandeel oil, have been measured in supercritical carbon dioxide experimentally. The measurements were performed at the temperatures of 313.2 and 343.2 K in the pressure range of 8 to 26 MPa. Experimental temperatures, pressures, and densities of the equilibrium phases are tabulated. The K-values of the ethyl esters of docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and oleic acid of the urea-fractionated mixture are compared with previously published experimental binary and multicomponent data on the same mixture before performing the urea-fractionation. K-value data of this type are essential to conceive proper equipment design for separation of the various polyunsaturated ω-3 fatty acids present in fish oil as esters.     

Process conditions for separating fatty acid esters by supercritical CO2

The solubilities of ethyl palmitate, ethyl oleate, ethyl eicosapentaenoate (EPA) and ethyl docosahexaenoate (DHA) in supercritical carbon dioxide were determined by a continuous flow method. The solubilities of fatty acid ethyl esters increased with pressure and decreased as the temperature was increased. An empirical equation, similar to Chrastil's equation, was used to describe the relationship between solute solubility and the density of carbon dioxide. The empirical equation was further used to qualitatively estimate the separation efficiency of isolating EPA and DHA ethyl esters from fatty acid esters. The operating conditions yielding high solubility gave fast extraction rate but resulted in low separation efficiency. Experiments were conducted to separate ethyl EPA and ethyl DHA from a model mixture containing four fatty acid ethyl esters and from esterified squid visceral oil. The experimental data compared closely with the calculated values.     

Solubility of Jatropha and Aquilaria oils in supercritical carbon dioxide at elevated pressures

This study investigated experimental equilibrium solubilities of Jatropha curcas and Aquiliaria crassna oils dissolved in supercritical carbon dioxide at temperatures of 318-338 K and pressures of 20, 25, 30, 35 MPa. The highest solubility of J. curcas and A. crassna oil were 29.8 and 28.4 mg L⁻¹, respectively, at 338 K and 35 MPa. The oil solubilities and the concentration of triglycerides both increased with increasing temperature and pressure. Triglyceride molecules surrounded by carbon dioxide molecules may be proposed since solubilities increased with the flux of supercritical carbon dioxide. The solubility of these two oils linearly increased with the density of supercritical carbon dioxide. Experimental data of the oil solubility were successfully correlated by the Chrastil equation.     

邻羟基苯甲酸和邻甲氧基苯甲酸在超临界CO2中的溶解度研究

采用流动法测定和研究了邻羟基苯甲酸和邻甲氧基苯甲酸在308K、328K下,10．0～24．0MPa范围内,在纯超临界CO2中的溶解度,并简要分析分子极性和结构特点对固体溶质溶解度大小的影响。同时,将超临界流体视为膨胀液体,根据溶液理论,建立了计算溶质在超临界流体中溶解度的膨胀液体模型。应用该模型对试验数据进行回归,得到了令人满意的结果。     

苯甲酸在含不同夹带剂的超临界CO2中的溶解度

利用流动法分别测定了苯甲酸在温度308.15, 318.15, 328.15 K、压力范围8.0~23.0 MPa时,在纯超临界CO2及以乙醇、乙酸乙酯、乙二醇为夹带剂的超临界CO2中的溶解度. 研究结果表明,三种夹带剂的加入均可以不同程度地提高苯甲酸的溶解度,其增大幅度为乙醇>乙二醇>乙酸乙酯. 此外还探讨了温度、压力对苯甲酸在超临界CO2中溶解度的影响,以及夹带剂的作用机理,并用Sovova方程对实验数据进行回归,得到了较满意的结果.     

Vapor-liquid equilibrium behavior of the ethane—n-butane—n-hexane system

A high pressure visual cell was designed and constructed for the study of vapor-liquid equilibria of rnulticomponmt systems at elevated temperatures and pressures. One of the unique features of this vapor-liquid equilibrium cell facility resides in the ability to measule pressures using a transducer connectcd directly to the equilibrium chamber of this cell. In addition, the design of this cell, incorporated the capability to permit the withdrawal of vapor and liquid microsamples from the respective phases in equilibrium. The composition of these microsamples was established with a gas chromatographic facility provided with a thermal conductivity detector. The overall performance of this vapor-liquid equilibriiini facility was tested on the system ethane-n-butane for which reliable vapor-liquid equilibrium data are already available in the literature. Five different charges of the ethane-n-butane-n-hexane system were investigated with this facility for temperatures ranging from 48.3 up to 143.5°C and pressures up to 7619 kPa (75.19 atm). For these conditions, K-values were established from the experimental measurements on this ternary system. K-values calculated using the BWR-method for conditions corresponding to the experimental measurements produced K-constants that were in good agreement with the measured values. For these calculations, the original BWR-equation, constants and mixing rules were employed.     

Supercritical fluid extraction of vegetable oil seeds

The extraction of oil from canola seeds using supercritical carbon dioxide was investigated. The basic equations which govern the oil extraction from a bed of seeds were derived from first principles. The equations can be solved by standard numerical techniques using experimentally determined parameters for the concentration of oil in the solvent in equilibrium with seeds having a known oil content. Preliminary extraction rate data and equilibrium data are given for crushed canola seed during extraction using supercritical carbon dioxide at select temperatures and pressures. The research is directed at obtaining the basic information required for the design of continuous countercurrent extractors.     

Correlation and estimation of solubilities of fatty acids in supercritical carbon dioxide using solution model approach

In this study, solid solubility data of five fatty acids in supercritical carbon dioxide (CO₂) at different temperatures and pressures are correlated using a two-parameter solution model developed from the regular solution model coupled with the Flory⿿Huggins equation. The developed solution model with fewer parameters yields correlated results comparable to those from commonly used semi-empirical equations. In addition, both parameters in the solution model can be further generalized with the chain length of fatty acids and a new predictive solution model is proposed for solubility prediction. The predictive solution model proposed in this study provides better predicted results and yields average deviation in predicted solubilities of 22.1%. To further apply this solution model to other compounds, solid solubility data of three triglycerides in supercritical CO₂ at 313 K are also correlated. After model simplification and generalization, a new predictive solution model for triglycerides is also proposed, which yields average deviation in predicted solubilities of 29.8%. These results demonstrate that the solution model used in this study is applicable for correlation and prediction of solid solubilities of structure-related compounds in supercritical CO₂.     

超临界流体萃取的平衡溶解度

由溶剂化缔合观点,推导出了计算难挥发物质在超临界流体(SCF)中平衡溶解度的缔合模型.利用文献数据对缔合模型的适用性进行了考察,得到了较满意的结果.以缔合模型为基础,对SCF的溶解能力及其随诸因素影响的变化规律进行了分析和讨论,由此得出的一些推论均能和实验现象一致.     

Coupled Supercritical Fluid Extraction/Chromatography of Polycyclic Aromatic Hydrocarbons: Correlation with Solubility Calculations

The solubility of: naphthalene, fluorene, phenanthrene, pyrene, and chrysene in supercritical CO₂ at two temperatures and pressures up to 200 atm were calculated from fugacities derived via the Peng-Robinson equation of state. The calculated solubilities were correlated with the results of experiments in which polycyclic aromatic hydrocarbons (PAH) in fuel mixtures were extracted with supercritical CO₂ and analysed by supercritical fluid chromatography and by gas chromatography.     

分散红73和分散蓝183及其混合物在超临界二氧化碳中溶解度的测定与关联(英文)

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology. In this study, solubilities of C.I. Disperse Red 73, C.I. Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method. Under the experimental conditions for the binary (C.I. Disperse Red 73 + CO2 or C.I. Disperse Blue 183 + CO2) and ternary (C.I. Disperse Red 73 + C.I. Disperse Blue 183 + CO2) systems, the solubilities increase with pressure. The solubility of C.I. Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa, and the trend is opposite when the pressure is higher than 16 MPa. However, there is no crossover pressure for C.I. Disperse Red 73. The solubilities are also affected by molecular polarity of dyes. The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their disso-lution in supercritical CO2. The experimental data of solubilities of C.I. Disperse Red 73, C.I. Disperse Blue 183, and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.     

THE SOLUBILITY OF PARAFFINIC HYDROCARBONS AND THEIR DERIVATIVES IN SUPERCRITICAL CARBON DIOXIDE

The solubilities of twenty-five paraffinic model compounds, octadecane (C₁₈H₃₈) through tetracosane (C₂₄H₅₀) and related monofunctional derivatives, were measured in supercritical carbon dioxide at 310 and 320 K. The derivatives included sulfides, amines, phosphines, ketones and other functional groups. Several of the solutes were liquids at the extraction temperatures and pressures, and both liquid and fluid phase binary composition data are reported in some cases. A systematic attempt was made to explore how the presence of a particular functional group on the solute molecule affected the solubility of the compound relative to the parent hydrocarbon of equivalent chain length.     

Effects of polymers as direct CO2 thickeners on the mutual interactions between a light crude oil and CO2

In this paper, two commercial polymers with relatively low molecular weights, poly vinyl ethyl ether (PVEE) and poly 1-decene (P-1-D), are tested as direct thickeners for CO₂ and their detailed effects on the mutual interactions between a light crude oil and polymer-thickened CO₂ are experimentally studied under different reservoir pressures. More specifically, the polymer cloud-point pressures are measured at different known polymer solubilities in supercritical CO₂. The equilibrium interfacial tensions (IFTs) and onset pressures of quick polymer dissolution into CO₂ are measured for the polymer?pure CO₂ systems. The polymer-swelling effect due to pure CO₂ dissolution is observed and examined. To study the mutual interactions between the light crude oil and polymer-thickened CO₂, their equilibrium IFTs are measured and their so-called minimum miscibility pressures (MMPs) and onset pressures of the initial quick light-hydrocarbons extraction by CO₂ are determined. The oil-swelling effect due to polymer-thickened CO₂ dissolution is also visualized and analyzed. All the experimental data for polymer-thickened CO₂ are compared with those for pure CO₂.     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Supercritical carbon dioxide fractionation of fish oil fatty acid ethyl esters

Fractionation of fish oil fatty acid ethyl esters was investigated with the aim of obtaining a lipid fraction enriched in ω-3 fatty acids and with a suitable EPA/DHA ratio. The results obtained highlight the possibility of modifying the original fatty acid ethyl esters concentration by optimizing the extraction conditions in terms of pressure, temperature, and supercritical carbon dioxide flow rate. Supercritical fluid fractionation (SFF) appears to be a useful processing technique for changing the composition of lipids in order to obtain high value functional products. The use of proper fractionation temperatures and pressures along the column influenced the solvent-to-feed ratio to obtain fractions with suitable composition for market requirements.     

THE SOLUBILITY OF PARAFFINIC HYDROCARBONS AND THEIR DERIVATIVES IN SUPERCRITICAL CARBON DIOXIDE

The solubilities of twenty-five paraffinic model compounds, octadecane (C₁₈H₃₈) through tetracosane (C₂₄H₅₀) and related monofunctional derivatives, were measured in supercritical carbon dioxide at 310 and 320 K. The derivatives included sulfides, amines, phosphines, ketones and other functional groups. Several of the solutes were liquids at the extraction temperatures and pressures, and both liquid and fluid phase binary composition data are reported in some cases. A systematic attempt was made to explore how the presence of a particular functional group on the solute molecule affected the solubility of the compound relative to the parent hydrocarbon of equivalent chain length.     

Separation of Phenantrene from Anthracene Oil using Supercritical Carbon Dioxide

Supercritical fluid extraction (SFE) is a relatively new separation technique that has received much attention in recent years. This process is an alternative to distillation or liquid extraction. Its main advantage over the conventional ones is that the dissolved extract may be completely separated from the supercritical fluid simply by decreasing the pressure. In recent years considerable effort has been devoted to the measurement of equilibrium solubility data for solids in supercritical fluids. A coal tar distillate, anthracene oil, which contains 34.46 mass‐% phenanthrene, 33.8 mass‐% anthracene, 13.89 mass‐% carbazole and other impurities, was used as the model mixture. In this study, an experimental flow‐type apparatus has been designed to determine solubility data for the main components of anthracene oil (phenanthrene, anthracene, and carbazole) as a binary, quaternary, and multi component mixture in supercritical carbon dioxide. The equilibrium solubilities were measured at 45 °C isotherm, over a pressure range of 98–200 bar. The separation of phenanthrene from anthracene oil has been also studied by supercritical carbon dioxide at different temperatures and pressure in an extracting vessel containing 27 sieve trays.     

Simulation modeling of the phase behavior of palm oil-supercritical carbon dioxide

The phase behavior of crude palm oil (CPO) with supercritical CO₂ was successfully modeled in an Aspen Plus^® 10.2.1 commercial simulator (Aspen Technology Inc., Cambridge, MA) using the Redlich-Kwong-Aspen (RKA) equation of state thermodynamic model. The modeling procedure involved estimating pure component vapor pressures and critical properties and computing a regression of phase equilibrium behavior. The interaction parameters for the RKA model were obtained from the regression of experimental phase equilibrium data for a binary system of palm oil components-supercritical CO₂ available in the literature. The distribution coefficients and solubilities of palm oil components obtained from this simulation showed good agreement with experimental data obtained from the literature. The model provides an efficient and cost-effective alternative for the preliminary design and optimization of a supercritical fluid extraction process involving a complex CPO-supercritical CO₂ system.     

苯酚在亚临界及超临界CO_2中溶解度的测定

利用流动法高压相平衡装置,测定了苯酚(固态)在亚临界和超临界CO_2中的溶解度.实验是在303-312K,8.5—50MPa的范围内进行.将实验数据与SRK和PR状态方程进行关联,得到了较好的结果.     

High-pressure phase behavior of carbon dioxide in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Phase equilibrium data of carbon dioxide in the ionic liquid 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]) are presented at high pressures up to about 30 MPa and at temperatures between 298.15 K and 343.15 K. The solubilities at a given temperature were determined by measuring the bubble point pressure of the ionic liquid solution with carbon dioxide dissolved using the high-pressure equilibrium apparatus equipped with a variable-volume view cell. Solubility results are reported for carbon dioxide concentrations ranging from 0.21 up to 0.80 mole fraction. Carbon dioxide gave very high solubilities in the ionic liquid at lower pressures, while the equilibrium pressure increased very steeply at higher concentrations of carbon dioxide. The solubility of carbon dioxide in the ionic liquid decreased with an increase in temperature.