Extraction of jojoba seed oil using supercritical CO2+ethanol mixture in green and high-tech separation process

In this study, the extraction of jojoba seed oil obtained from jojoba seed using both supercritical CO₂ and supercritical CO₂+ethanol mixtures was investigated. The recovery of jojoba seed oil was performed in a green and high-tech separation process. The extraction operating was carried out at operating pressures of 25, 35 and 45 MPa, operating temperatures of 343 and 363 K, supercritical fluid flow rates of 3.33 × 10⁻⁸, 6.67 × 10⁻⁸ and 13.33 × 10⁻⁸ m³ s⁻¹, entrainer concentrations of 2, 4 and 8 vol.%, and average particle diameters of 4.1 × 10⁻⁴, 6.1 × 10⁻⁴, 8.6 × 10⁻⁴ and 1.2 × 10⁻³ m. It was found that a green chemical modifier such as ethanol could enhance the solubilities, initial extraction rate and extraction yield of jojoba seed oil from the seed matrix as compared to supercritical CO₂. In addition, it was found that the solubility, the initial extraction rate and the extraction yield depended on operating pressure and operating temperature, entrainer concentration, average particle size and supercritical solvent flow rate. The solubility of jojoba seed oil and initial extraction rate increased with temperature at the operating pressures of 35 and 45 MPa and decreased with increasing temperature at the operating pressure of 25 MPa. Furthermore, supercritical fluid extraction involved short extraction time and minimal usage of small amounts entrainer to the CO₂. About 80% of the total jojoba seed oil was extracted during the constant rate period at the pressure of 35 and 45 MPa.     

Optimization of essential oil supercritical extraction from Algerian Myrtus communis L. leaves using response surface methodology

The present work deals with the application of the supercritical fluid extraction process to extract essential oils from the leaves of an Algerian myrtle plant (Myrtus communis L.). Using the surface response methodology, an optimization of the extraction recovery was carried out, varying the pressure in the range of [10–30 MPa], the temperature within [308–323 K], a solvent flow rate fixed at 0.42 kg h⁻¹ and a mean particle diameter equal to 0.5 mm or less than 0.315 mm. The maximum value of essential oil recovery relative to the initial mass of leaf powder was 4.89 wt%, and was obtained when the SC–CO₂ extraction was carried out under 313 K, 30 MPa and with a particle diameter less than 0.315 mm. A second-order polynomial expression was used to express the oil recovery. The calculated mass of recovered oil using the response surface methodology was very close to the experimental value, confirming the reliability of this technique.     

Supercritical carbon dioxide extraction of Gac oil

Supercritical carbon dioxide extraction of Gac (Momordica cochinchinensis Spreng) aril was performed at pressures ranging from 200 to 400 bar, temperatures from 313 to 343 K and specific flow rates from 50 to 90 kg h⁻¹ CO₂ kg⁻¹ Gac aril. Total oil recovery and carotenes concentration were investigated in the course of extraction. Mathematical modelling of oil solubility data was also performed. The results showed that at specific flow rate of 70 kg h⁻¹ kg⁻¹, pressure of 400 bar and temperature of 343 K, Gac oil recovery exceeded 95% after 120 min of extraction. Gac oil loading of supercritical carbon dioxide was successfully described by Chrastil's model. Carotenes concentration of extracted Gac oil was found at level of thousands of ppm.     

Supercritical production and fractionation of fatty acid esters and acylglycerols

The production of biodiesel or fatty acid esters (FAE) from lipids with supercritical methanol (scMeOH) has gained interest in the last decade because it allows the direct transesterification of crude oils and fats. The reaction should be carried out above 593 K in order to achieve complete conversion. When milder conditions are set, also monoglycerides (MG) and diglycerides (DG), together with glycerol, are obtained as byproducts of the transesterification process. Acylglycerols are common food emulsifiers and surface active agents in many industrial cleaning products.The main goal of this work is to study the fractionation of FAE and acylglycerols by using CO₂ as a green solvent. Mixtures of FAE, MG and DG were produced by partial transesterification of sunflower oil with scMeOH in a temperature range of 556–605 K and using different methanol to oil molar ratios (between 20 and 50). Then, experimental data on phase equilibria of reaction products + CO₂ were measured at 298 K and 313 K in a variable volume cell with windows. The measured data were used to test the predictive capability of the Group Contribution with Association Equation of State (GCA-EoS). The acylglycerols can be purified by near critical extraction of the FAE with CO₂. The simulation of the extraction process working with CO₂, in liquid or supercritical state, gives a concentration of acylglycerols higher than 99.8 wt.% in the raffinate phase with a concentration of FAE above 97 wt.% in the extract phase.     

Measurement and modeling of the phase behavior of the (carbon dioxide + water) mixture at temperatures from 298.15 K to 448.15 K

An analytical apparatus has been designed to study the phase behavior of fluid mixtures of relevance to CO₂-enhanced oil recovery and carbon dioxide storage in deep aquifers or depleted oil fields. The fluid phases are circulated by means of a dual-channel magnetically-coupled pump and aliquots may be withdrawn from the re-circulation loops, by means of high-pressure sampling valves, for analysis by gas chromatography. The high-pressure cell is fitted with a special probe that may be rotated in order to draw liquid into the re-circulation loop from different heights within the cell, thereby permitting the study of three-phase vapor–liquid–liquid equilibria. The working temperature range of the apparatus is from (298 to 448) K and the maximum working pressure is 50 MPa.In this work, measurements have been made on the binary system (CO₂ + H₂O) at temperatures from (298.15 to 448.15) K and pressure from (1.5 to 18.0) MPa, and the results are compared with the available literature data. Vapor–liquid–liquid and liquid–liquid equilibrium points were also measured at T = 298.15 K. Standard uncertainties were 0.04 K for temperature, 0.04% of reading for pressure, and typically 3 × 10⁻⁴ and 8 × 10⁻⁴ for the mole fractions in liquid and vapor phases respectively. The results have been correlated by means of an asymmetric approach based on the Peng–Robinson equation of state, for the vapor phase, and an extended form of Henry's law incorporating the NRTL solution model, for the aqueous liquid-phase. The ability of the Krichevsky–Kasarnovsky (KK) approach to correlate the data has also been evaluated.     

Liquid and supercritical CO2 extraction of fat from rendered materials

The separation of fat from rendered materials has potential for value-added products, fuels and feed sources for animals. Current industrial processes utilize continuous screw pressing to extract fat from rendered materials, but the ability to minimize residual fat content is limited. In this work, liquid and supercritical CO₂ were used to extract the remaining fat from rendered poultry meal. CO₂ extraction offers high extraction yields with potential ecological and economic benefits for the rendering industry. A semi-batch extraction unit was used to investigate the effect of pressure (69–345 bar), temperature (25 °C, 40 °C and 50 °C), flow rate, and mass of CO₂ on the extraction yield and the fat solubility. Maximum extraction yields between 87% and 97% were obtained which produced a remaining fat content of 1.0 ± 0.3 wt% in the extracted poultry meal. Fat solubility increased with pressure but decreased with temperature, providing liquid CO₂ with the highest fat solubility (6.47 g/L) at 25 °C and 345 bar. The Chrastil model successfully correlated the solubility data as a function of density and temperature, obtaining an AARD value of 5.56%. Gas chromatography was used to analyze the composition of fatty acids, obtaining similar results with those reported in the literature. It can be concluded that high fat extraction yields can be obtained using CO₂ and that liquid CO₂ is more effective than supercritical CO₂ for the extraction of rendered fats under the conditions tested.     

Phase equilibrium of two CO2+ biodegradable oil systems up to 72 MPa

A setup based on a static visual synthetic method for determining phase equilibria up to 100 MPa is presented. Solubilities of carbon dioxide (CO₂) in a high-oleic sunflower oil (HOSO) and in an additivated vegetable lubricant (BIO-2T-05) were determined from 298 K to 363 K up to CO₂ mass compositions of 0.42. The experimental device was verified comparing the solubilities of CO₂ in HOSO with values from other laboratory. For both systems, the values of CO₂ solubility show cross-over pressures among the different isotherms. A new equation was used to correlate the solubility data, with deviations in CO₂ mole fraction in the oil-rich phase lower than 1.6%. The prediction ability of Carvalho and Coutinho equation was tested with experimental data. Vapor–liquid–liquid equilibria were also investigated for CO₂ + BIO-2T-05 in the range 288–305 K. Furthermore, densities and viscosities at 0.1 MPa for BIO-2T-05 were measured from 278 K to 373 K.     

Phase equilibria of (CO2 + H2O + NaCl) and (CO2 + H2O + KCl): Measurements and modeling

We report experimental measurements of the phase behavior of (CO₂ + H₂O + NaCl) and (CO₂ + H₂O + KCl) at temperatures from 323.15 K to 423.15 K, pressure up to 18.0 MPa, and molalities of 2.5 and 4.0 mol kg⁻¹. The present study was made using an analytical apparatus and is the first in which coexisting vapor- and liquid-phase composition data are provided. The new measurements are compared with the available literature data for the solubility of CO₂ in brines, many of which were measured with the synthetic method. Some literature data show large deviations from our results.The asymmetric (γ–φ) approach is used to model the phase behavior of the two systems, with the Peng–Robinson equation of state to describe the vapor phase, and the electrolyte NRTL solution model to describe the liquid phase. The model describes the mixtures in a way that preserves from our previous work on (CO₂ + H₂O) the values of the Henry's law constant and the partial molar volume of CO₂ at infinite dilution Hou et al. [22]. The activity coefficients of CO₂ in the aqueous phase are provided. Additionally, the correlation of Duan et al. [14] for the solubility of CO₂ in brines is tested against our liquid-phase data.     

Phase equilibrium data of guaçatonga (Casearia sylvestris) extract + ethanol + CO2 system and encapsulation using a supercritical anti-solvent process

The aim of this research was to investigate the phase equilibrium behavior of a system containing guaçatonga extract + ethanol + CO₂ in order to help define the adequate conditions of temperature and pressure for the co-precipitation process, performed by means of supercritical anti-solvent (SAS) technique. Guaçatonga (Casearia sylvestris) is a native medicinal plant from Brazil, rich in valuable components such as β-caryophyllene, α-humulene and bicyclogermacrene. Phase equilibrium data were obtained by the static method using guaçatonga extract dissolved in ethanol (1:100, wt/wt), at temperatures ranging from 35 to 75 °C and CO₂ mass content from 60 to 90 wt%. It was noticed that the system exhibited solid–vapor–liquid, solid–liquid–liquid and solid–vapor–liquid–liquid transition types and a lower critical solution temperature behavior. Phase behavior study was considered for the definition of the SAS conditions applied for the encapsulation of guaçatonga extract in the biopolymer Pluronic F127. The conditions tested ranged from 80 to 140 bar at 45 °C. At 80 bar only segregated particles of extract and the biopolymer were detected, while at 110 and 140 bar an extract encapsulation was achieved.     

Extraction of sunflower oil with supercritical CO2: Experiments and modeling

Extraction of sunflower oil from sunflower seeds (Heliantus annuus L.) using supercritical CO₂ was studied. The shrinking core model was applied to the modeling of the packed-bed extraction process. The experimental data were obtained for extraction conducted at the pressures of 20, 30, 40, 50 and 60 MPa; the temperatures of 313, 333 and 353 K, the CO₂ flow rates of 1–4, and 6 cm³ CO₂ min⁻¹; the mean particle diameters of 0.23, 0.55, 1.09, 2.18 mm. The supercritical CO₂ extraction process was modeled by a quasi steady state model as a function of extraction time, pressure, temperature, CO₂ flow rate, and particle diameter. The supercritical CO₂ extraction process. The intraparticle diffusion coefficient (effective diffusivity) D_e was used as adjustable parameter. The model using the best fit of D_e was correlated the data satisfactorily.     

Supercritical CO2 oilseed extraction in multi-vessel plants. 2. Effect of number and geometry of extractors on production cost

The objective of this work was to study production costs for the supercritical CO₂ extraction of a pre-pressed oilseed (packed bed with 2-mm particles) in a 2-m³ industrial multi-vessel plant operating at 40 °C and 30 MPa, using a fully predictive mass transfer model to simulate the process. We modified the inner diameter (47.3 ≤ D ≤ 65.6 cm) and number (n = 2, 3, or 4) of extraction vessels, and the mass flow rate of CO₂ (Q = 3000 or 6000 kg/h), thus changing the aspect ratio of the extraction vessels (3 ≤ L/D ≤ 8), and superficial velocity (2.71 ≤ U ≤ 10.8 mm/s) and specific mass flow rate (6 ≤ q ≤ 24 kg/h per kg substrate) of CO₂. Production cost decreased when increasing the mass flow rate of CO₂ or the number of extraction vessels (or when increasing q). Production cost did not depend on the geometry of extraction vessel for a constant specific mass flow rate of CO₂, but it decreased with a decreasing of the L/D ratio of the vessel for a constant superficial velocity of CO₂. For any given plant, the contribution of fixed cost items (capital, labor) to the production cost increased with extraction time, unlike that of variable cost items (substrate, CO₂, energy), which decreased. Thus, there was an optimal extraction time that minimized production cost for each plant. This work proposes an expression for capital cost of an industrial multi-vessel plant as a function of the mass flow rate of CO₂ (which defines the cost of the solvent cycle of the plant), and the volume of the extraction vessels (which together with number of extraction vessels define the cost of extraction section of the plant), with a scaling factor of 0.48 for both items. Under optimal conditions, capital cost represented 30–40% of the production cost, but uncertainties in capital cost estimates (about ±50% using the proposed expression) may largely affect these estimates. The lowest production cost estimated in this work was USD 7.8/kg oil for the extraction of prepressed oilseed in a four-vessel plant using 6000 kg/h of CO₂. The mass flow rate of CO₂ and number of extraction vessels also affected annual productivity that was about 360 ton oil for the same plant operating 7200 h per year. Oil yields were above 90% for both three- and four-vessel plants.     

Lycopene solubility in mixtures of carbon dioxide and ethyl acetate

In order to improve the efficiency of processes using supercritical (sc) carbon dioxide (CO₂) to micronize the carotenoid “lycopene”, it is important to know the solubility of lycopene in mixtures of the organic solvent ethyl acetate (EA) and the antisolvent CO₂ at elevated pressures. The solubility of lycopene has been determined for different temperatures (313–333 K), pressures (12–16 MPa) and CO₂ molar fractions (0.58–1). The obtained data show that CO₂ acts as an antisolvent in the system lycopene/EA/CO₂ in the range of CO₂/EA ratios studied. The solubility of lycopene is rather small with lycopene molar fractions ranging from 0.1 × 10⁻⁶ to 46 × 10⁻⁶. The solubility of lycopene increases with temperature, pressure and EA concentration.     

Optimization of supercritical fluid extraction of phytosterol from roselle seeds with a central composite design model

Recovery of phytosterol from roselle (Hibiscus sabdariffa L.) seeds via supercritical carbon dioxide extraction modified with ethanol was investigated at pressures of 200–400 bar, temperatures from 40 to 80 °C and at supercritical fluid flow rates from 10 to 20 ml/min. It was found that an entrainer such as ethanol could enhance the solubility and extraction yield of roselle seed oil from the seed matrix, compared to values obtained using supercritical CO₂. After a typical run (holding period of 30 min, continuous flow extraction of 3 h), the results indicate that the oil recovery was optimal with a recovery of 108.74% and a phytosterol composition of 7262.80 mg kg^?1 at relatively low temperature of 40 °C, a high pressure of 400 bar and at a high supercritical fluid flow rate of 20 ml/min in the presence of 2 ml/min EtOH as entrainer. The solubility of roselle seed oil increased with temperature at the operating pressures of 200, 300 and 400 bar. Supercritical fluid extraction involved a short extraction time and the minimal usage of small amounts of entrainer in the CO₂.     

Phase behavior measurement for poly(isobornyl acrylate) + cosolvent systems in supercritical solvents at high pressure

We have conducted experiments to obtain cloud-point data of binary and ternary mixtures for poly(isobornyl acrylate) [P(IBnA)] (Mw = 100,000) + isobornyl acrylate(IBnA) in supercritical carbon dioxide (CO₂), P(IBnA) (Mw = 100,000) + dimethyl ether (DME) in CO₂, P(IBnA) (Mw = 100,000) in propane and butane, and P(IBnA) (Mw = 1,000,000) in propane, propylene, butane and 1-butene at high pressure conditions. Phase behaviors for these systems were measured at a temperature range from 323.4 K to 474.1 K and pressure up to 296.7 MPa. The cloud-point curves of P(IBnA) (Mw = 100,000) + IBnA and DME in CO₂ change from upper critical solution temperature (UCST) behavior to lower critical solution temperature (LCST) behavior as IBnA and DME concentration increases, and liquid–liquid–vapor phase behavior appears for the P(IBnA) (Mw = 100,000) + CO₂ + 80.3 wt.% IBnA system. Phase behaviors of P(IBnA) and 50 wt.% IBnA in CO₂ and P(IBnA) in propane and butane show the pressure difference in accordance with Mw = 1,000,000 and Mw = 100,000 of P(IBnA). Also, the solubility curves for IBnA in supercritical CO₂ were measured at a temperature range of (313.2–393.2) K and pressure up to 22.86 MPa. The experimental results were modeled with the Peng–Robinson equation of state (PR-EOS) using a mixing rule including two adjustable parameters. The critical property of IBnA is estimated with the Joback–Lyderson method.     

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.     

Experimental measurement and modelling with Aspen Plus® of the phase behaviour of supercritical CO2 + (n-dodecane + 1-decanol + 3,7-dimethyl-1-octanol)

Experimental phase equilibrium data for the systems CO₂ + n-dodecane, CO₂ + 1-decanol and CO₂ + 3,7-dimethyl-1-octanol were used to determine values for binary interaction parameters for use in the RK-ASPEN thermodynamic model in Aspen Plus^®. Bubble and dew point data of the mixtures CO₂ + (n-dodecane + 1-decanol), CO₂ + (n-dodecane + 3,7-dimethyl-1-octanol), CO₂ + (1-decanol + 3,7-dimethyl-1-octanol) and CO₂ + (n-dodecane + 1-decanol + 3,7-dimethyl-1-octanol) were measured experimentally in a static synthetic view cell, and compared to the data predicted by the RK-ASPEN model. The model predicted the phase equilibrium data reasonably well in the low solute concentration region; significant deviation of model predictions from experimental data occurred in the mixture critical and high solute concentration regions due to the exclusion of solute–solute interaction parameters in the model. Distribution coefficients and separation factors were determined for the multi-component mixture and separation of the alkane from the alcohol mixture with a supercritical fluid extraction process was found to be possible.     

Removal of contaminants from polluted drilling mud using supercritical carbon dioxide extraction

Liquid drilling fluid is often called drilling mud is heavy, viscous fluid mixtures use to carry rock cuttings to the surface and lubricate and cool the drill bit. During carrying cuttings they contaminated which not only reduce their functionality but also make them a hazardous and dangerous wastes which cannot be discharged anywhere without treatment. Due to this fact, in the present study, supercritical extraction process was used to remove contaminants from the drilling mud. Regarding this, effect of different parameters including extraction temperature (313–338 K) and pressure (100–200 bar), flow rate of CO₂ (0.05–0.36 cm³/s) and static time (20–130 min) on the removal of contaminations from drilling mud was examined using the design of experiment of changing one factor at a time. The obtained results revealed that the optimum operational conditions that lead to the highest removal degree of contaminations are temperature and pressure of 333 K and 180 bar, respectively, flow rate of lower than 0.1 cm³/s and the static time of 110 min. In addition, to examine the effect of the supercritical extraction on the crystalline structure modification and removal contaminations X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were performed which confirmed the successful removal of contaminations from the drilling mud without significant crystalline modification.     

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.     

Extraction of rotundifuran and casticin from chaste tree fruits by near critical liquid carbon dioxide

In this study we investigated the use of near critical liquid CO₂ for the extraction of chaste tree ripe fruits (Vitex agnus-castus L.). Two procedures utilizing near critical liquid CO₂ were tested: (1) the extraction of plant material via continuous solvent recycling and (2) the extraction by a Soxhlet-type process via periodic solvent recycling. The results were compared with data obtained from the traditional Soxhlet extraction process using three different solvents, namely n-hexane, dichloromethane, and methanol. Extractions with liquid CO₂, recycled in continuous mode, of chaste tree fruits in three sizes: (1) <0.3 mm, (2) 0.3–0.8 mm, and (3) 3–3.2 mm resulted in maximum yields of 4.9%, 4.1% and 2.8%, respectively. Extraction times of 0.17–25 h were used. Extraction by continuous recycling of liquid CO₂ is more efficient than Soxhlet-type periodic recycling of liquid CO₂, resulting in up to three times higher yield for the same solvent-to-feed ratio. Comparison of HPLC data for extracts obtained by liquid CO₂, n-hexane, dichloromethane and methanol showed that the diterpene rotundifuran is best extracted by liquid CO₂ (3.010 g/kg drug), and the flavonoid casticin is best extracted by n-hexane (1.067 g/kg drug).     

Hydrogen-storage properties of MgH2–10Ni–2NaAlH4–2Ti prepared by reactive mechanical grinding

A sample of 86 wt% MgH₂–10 wt% Ni–2 wt% NaAlH₄–2 wt% Ti (named MgH₂–10Ni–2NaAlH₄–2Ti) was prepared by reactive mechanical grinding. Activation of the sample was not required at 573 K. At the first hydriding–dehydriding cycle (n = 1), the sample absorbed more than 5 wt% H at 573 K under 12 bar H₂ for 60 min. The hydriding rate increased as the temperature increased from 423 K to 553 K. MgH₂–10Ni–2NaAlH₄–2Ti showed quite high hydridng rates at relatively low temperatures of 423 K and 473 K under 12 bar H₂, absorbing 4.02 wt% H for 60 min at 473 K.