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.     

Supercritical CO2 extraction of bioactive Tyrian purple precursors from the hypobranchial gland of a marine gastropod

Supercritical CO₂ provides considerable advantages over traditional solvents for the extraction of bioactive compounds from organic matter. Here we demonstrate the use of supercritical CO₂ as an efficient and safe alternative to traditional solvent extraction for the recovery of bioactive Tyrian purple precursors tyrindoleninone, 6-bromoisatin and tyriverdin from the marine mollusc Dicathais orbita. The effect of pressure on the selective extraction of brominated indoles was tested at 15, 30 and 50 MPa CO₂, and was compared to traditional chloroform extract composition and yields. Extracts obtained from 15 MPa selectively concentrated 6-bromoisatin, at 78% of the extract composition, whereas increased pressures of 30 and 50 MPa increased the solvating power of supercritical CO₂ to include the more lipophilic tyrindoleninone at 35 and 29% respectively, and tyriverdin at 23 and 40% respectively. This extraction method was also effective in separating the brominated indoles from toxic choline esters in the mollusc extracts. Extract yields from supercritical CO₂ were comparable to solvent extraction relative to whole whelk weight. This provides a viable alternative for nutraceutical development that does not rely on the use of toxic solvents.     

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.     

Response surface optimization of Smyrnium cordifolium Boiss (SCB) oil extraction via supercritical carbon dioxide

In this study, the essential oil of aerial parts of a species of a plant called Smyrnium cordifolium Boiss (SCB) was extracted by supercritical CO₂. The essence was analyzed by the method of GC/MS. Design of experiments was carried out with response surface methodology by Minitab 16 software to optimize four operating variables of supercritical carbon dioxide (SC-CO₂) extraction (pressure, temperature, CO₂ flow rate and extraction dynamic time). This is the first report announcing optimization of the operation of supercritical extraction of SCB in laboratorial conditions. Optimizing process was done to achieve maximum yield extraction. Independent variables were dynamic time (t_d), pressure (P), temperature (T) and flow rate of SC-CO₂ (Q) in the range of 30–150 min, 10–30 MPa, 40–60 °C and 0.5–1.7 ml/min, respectively. The experimental optimal recovery of essential oil (0.8431, w/w%) was obtained at 13.43 MPa, 40 °C, 150 min (dynamic) and 1.7 ml/min (CO₂ flow rate).     

Extraction of Epigallocatechin-3-gallate from green tea via supercritical fluid technology: Neural network modeling and response surface optimization

In this study the extraction of (−)-Epigallocatechin-3-gallate (EGCG) from Iranian green tea was investigated by supercritical CO₂ with ethanol as co-solvent. Design of experiments and modeling were carried out with response surface methodology by Minitab software. The HPLC analysis of the extracted samples was used in conjunction with response surface design to optimize four operating variables of supercritical CO₂ extraction (pressure, temperature, CO₂ flow rate and extraction dynamic time). Optimum recovery of EGCG (0.462 g/g) was obtained at 19.3 MPa, 43.7 °C, 106 min (dynamic) and 1.5 ml/min (CO₂ flow rate). Moreover, a three-layer artificial neural network was developed for modeling EGCG extraction from green tea. In this regard, different networks (by changing the number of neurons in the hidden layer and algorithm of network training) were compared with evaluation of networks accuracy in extraction recovery prediction. Finally, the Levenberg–Marquardt algorithm with the six neurons in the hidden layer has been found to be the most suitable network.     

Micronization of salicylic acid and taxol (paclitaxel) by rapid expansion of supercritical fluids (RESS)

The particle sizes of the pharmaceutical substances are important for their bioavailability. The bioavailability can be improved by reducing the particle size of the drug. In this study, salicylic acid and taxol were micronized by the rapid expansion of supercritical fluids (RESS). Supercritical CO₂ and CO₂ + ethanol mixture were used as solvent. Experiments were carried out to investigate the effect of extraction temperature (318–333 K) and pressure (15–25 MPa), pre-expansion temperature (353–413 K), expansion chamber temperature (273–293 K), spray distance (6–13 cm), co-solvent concentration (ethanol, 1, 2, 3, v/v, %) and nozzle configuration (capillary and orifice nozzle) on the size and morphology of the precipitated salicylic acid particles. For taxol, the effects of extraction pressure (25, 30, 35 MPa) and co-solvent concentration (ethanol, 2, 5, 7, v/v, %) were investigated. The characterization of the particles was determined by scanning electron microscopy (SEM), optical microscopy, and LC–MS analysis.The particle size of the original salicylic acid particles was L/D: 171/29–34/14 μm/μm. Depending upon the different experimental conditions, smaller particles (L/D: 15.73/4.06 μm/μm) were obtained. The particle size of taxol like white crystal powders was reduced from 0.6–17 μm to 0.3–1.7 μm The results showed that the size of the precipitated salicylic acid and taxol particles were smaller than that of original particles and RESS parameters affect the particle size.     

Ovicidal activities of supercritical CO2 and N2O on Ascaris suum eggs

This study examined whether supercritical CO₂ and N₂O fluids are effective in inactivating Ascaris suum eggs, which were chosen as a model for parasite eggs. The treatments were carried out in a multibatch apparatus, in which, the eggs could be placed atop a solid surface (non-immersed condition) or in aqueous solution (immersed condition). Various CO₂ and N₂O phases—including gas (6 MPa, 30 °C), liquid (8 MPa, 30 °C), subcritical (10 MPa, 30 °C), and supercritical (10 MPa, 37 °C)—were tested with exposure times ranging from 1 to 20 min. Supercritical CO₂ and N₂O both showed a similar, strong ovicidal effect, requiring only 1 min in non-immersed conditions and 5 min in water-immersed conditions to achieve a 2.4-log inactivation. Subcritical CO₂ and N₂O showed a weaker ovicidal effect. The effect was significantly reduced for the gas and liquid phases, compared with the supercritical phases. This study reports that supercritical CO₂ and N₂O can be effectively employed as a non-thermal treatment technique to control parasite egg contamination in fecal matter and food.     

Extraction of bioactive enriched fractions from Eruca sativa leaves by supercritical CO2 technology using different co-solvents

Supercritical fluid extraction from freeze-dried Eruca sativa leaves is assessed with the aim of studying the feasibility to obtain bioactive enriched fractions containing different classes of valuable compounds. Total extraction yields and compositions using pure CO₂ and CO₂ + selected co-solvents are compared. Overall extraction curves, fitted by the model of broken and intact cells developed by Sovová, are reported and the influence of the main parameters that affect the extraction process is analysed. The extract with the highest content in glucosinolates and phenols was collected at 30 MPa and 75 °C using 8% (w/w) of water with respect to the CO₂ flow rate, whereas the fraction richest in lipids was obtained using 8% (w/w) of ethanol as co-solvent at 45 °C and 30 MPa. A process including a first step with supercritical CO₂ extraction using water as co-solvent followed by a second step, where a fraction rich in lipids is extracted using ethanol as co-solvent, is proposed. SCCO₂ results are compared with Soxhlet and other methods that combine organic solvents with ultrasounds.     

A shrinking core model and empirical kinetic approaches in supercritical CO2 extraction of safflower seed oil

Utilization of supercritical CO₂ in safflower seed extraction was performed using a semi-batch extractor. Different extraction parameters, such as 40–60 MPa pressure, 323–347 K temperature, 20–76 min time, and 1–3 mL/min CO₂ flow rate were applied. A two-stage experimental design application was performed in order to maximize the oil yield. First of all, a 3² factorial design was applied to estimate the effect of the main factors and their interactions. The second part of the experimental design was improved and accelerated using the steepest ascent method. Optimum extraction parameters were determined to be 50 MPa pressure, 347 K temperature and 76 min time at a constant CO₂ flow rate (3 mL/min) according to the 2² design. Under these conditions, the oil yield obtained was 39.42%, comparable with Soxhlet extraction (40%) for 8 h. Shrinking core and empirical kinetic models were applied in order to generalize the extraction process. The predicted data was compatible with the experimental data.     

Towards superhydrophobic coatings made by non-fluorinated polymers sprayed from a supercritical solution

The objective of this study was to create a superhydrophobic surface using polymers that are non-fluorinated and applying them to a surface via rapid expansion of a supercritical solution (RESS). Solubility studies of poly(ɛ-caprolactone) (PCL) and a statistical copolymer of vinyl acetate and vinyl pivalate (P(VAc-VPi))in supercritical carbon dioxide (scCO₂) were carried out using an extraction procedure. It was found that the most suitable process parameters for spraying these polymers using the RESS technique were 30 MPa, 40 °C and 10% (v/v) acetone as a co-solvent. The surfaces produced were characterized in terms of their morphology and hydrophobic properties by scanning electron microscopy and contact angle measurements, respectively. The most hydrophobic surfaces were obtained by spraying the P(VAc-VPi) copolymers, giving advancing water contact angles in the range of 120–155° due to the hydrophobic character of the polymer and the microstructure formed with the RESS technique. These results show great promise for the creation of superhydrophobic surfaces using non-fluorinated polymers applied to surfaces via RESS technique.     

Extraction of phenolic compounds and anthocyanins from blueberry (Vaccinium myrtillus L.) residues using supercritical CO2 and pressurized liquids

This work explored the potential of subcritical liquids and supercritical carbon dioxide (CO₂) in the recovery of extracts containing phenolic compounds, antioxidants and anthocyanins from residues of blueberry (Vaccinium myrtillus L.) processing. Supercritical CO₂ and pressurized liquids are alternatives to the use of toxic organic solvents or extraction methods that apply high temperatures. Blueberry is the fruit with the highest antioxidant and polyphenol content, which is present in both peel and pulp. In the extraction with pressurized liquids (PLE), water, ethanol and acetone were used at different proportions, with temperature, pressure and solvent flow rate kept constant at 40 °C, 20 MPa and 10 ml/min, respectively. The extracts were analyzed and the highest antioxidant activities and phenolic contents were found in the extracts obtained with pure ethanol and ethanol + water. The highest concentrations of anthocyanins were recovered with acidified water as solvent. In supercritical fluid extraction (SFE) with CO₂, water, acidified water, and ethanol were used as modifiers, and the best condition for all functional components evaluated was SFE with 90% CO₂, 5% water, and 5% ethanol. Sixteen anthocyanins were identified and quantified by ultra performance liquid chromatography (UPLC).     

Extraction of protocatechuic acid from Scutellaria barbata D. Don using supercritical carbon dioxide

The use of supercritical carbon dioxide (SC⿿CO₂), with water as a modifier, was evaluated in this study as a method to extract protocatechuic acid (PA) from Scutellaria barbata D. Don. The highest extraction yield of PA, 64.094 ± 2.756 μg/g of dry plant, was achieved at 75 °C and 27.5 MPa, with the addition of 15.6% (v/v) water as a modifier. The mean particle size was 0.355 mm, the CO₂ flow rate was 2.2 mL/min (STP) and the dynamic extraction time was 100 min. At pressures of 16.2⿿30.0 MPa and temperatures of 45⿿75 °C, the mole fraction solubilities of PA in SC⿿CO₂ ranged from 2.829 ÿ 10^⿿7 to 9.631 ÿ 10^⿿7. The solubility data for PA fit well in the Chrastil model. It is evident that the SC⿿CO₂ extraction uses less solvent, saves both energy and time and is an environmentally friendly extract technology that can be used in the food, cosmetic and pharmaceutical industries.     

Cosolvent-modified supercritical carbon dioxide extraction of phenolic compounds from bamboo leaves (Sasa palmata)

This study highlights the possibility of supercritical carbon dioxide for extracting phenolic compounds from bamboo leaves that have shown antioxidant and anticancer activities. The CO₂ extraction solvent was modified by adding ethanol–water mixture cosolvent of different concentrations to allow extraction of both polar and non-polar compounds. Conventional Soxhlet extraction was also done to investigate the advantages of supercritical extraction over the conventional extraction method. For addition of 5% (mol) of a 25:75 (mol:mol) ethanol–water mixture solvent to CO₂, the highest amount of polyphenols (7.31 ± 0.06 mg/g bamboo leaves in catechin equivalents) and radical scavenging activity (3.65 ± 0.05 mg/g bamboo leaves in BHA equivalents) at 20 MPa and 95 °C, could be obtained among the mixture cosolvents studied. For Soxhlet extraction with a 25:75 (mol:mol) ethanol–water mixture, 1.48 times the amount of phenolic compounds (10.85 ± 0.52 mg/g bamboo leaves in catechin equivalents), could be isolated compared with the supercritical extraction method, however, the radical scavenging activity (3.30 ± 0.05 mg/g bamboo leaves in BHA equivalents) was 0.90 times lower than the extract obtained from the supercritical extraction method. The seven major antioxidative compounds identified from the SC-CO₂ extraction method were: (1) dl-alanine, (2) gluconic acid, (3) phosphoric acid, (4) ß-siosterol, (5) β-amyrene, (6) α-amyrin acetate and (7) friedelin.     

Supercritical fluid extraction for quality control in beer industry

The knowledge of lipid composition in beer ingredients (malt and corn grits) and wort enables the quality control for final product. Since supercritical fluid extraction (SFE) is an efficient technique for preparing samples for analysis without the use of solvents, in this research Supercritical CO₂ (SC–CO₂) extraction was compared with the traditional Soxhlet one for a gravimetric determination of total lipids on malt and corn grits. The obtained extracts were then analyzed by HPLC-ELSD after TLC separation of triacylglycerols (TAGs) for lipids fingerprint. The extraction of total fats achieved by a 60-min run with pure CO₂ at 65 MPa and 100 °C was 43% higher than that produced by Soxhlet performed for 9 h for malt. The extraction was intermediate for SFE at 60 and 80 °C. The recovery of the TAG obtained with SC–CO₂ at 100 °C was statistically comparable with results from Soxhlet extraction.     

Production of polyphenol extracts from grape bagasse using supercritical fluids: Yield,extract composition and economic evaluation

The objective of this work was to determine the economic feasibility of large-scale operations of supercritical fluid extraction (SFE) for the recovery of phenolics using grape bagasse from Pisco residues. Experimental data were used to estimate the extraction kinetic parameters, as well as the cost of manufacturing the extracts. Experimental data were obtained using supercritical CO₂ containing 10% ethanol (w/w) at 313 K and 20–35 MPa. The supercritical CO₂/ethanol extraction process produced extracts with higher concentrations of phenolics than extracts produced using conventional techniques. The compounds identified in the extracts were syringic, vanillic, gallic, p-hydroxybenzoic, protocatechuic and p-coumaric acids, as well as quercetin. An evaluation of the economics of the process indicated the feasibility of an industrial SFE plant with a capacity of 0.5 m³ for producing an extract with an expected phenolics concentration of approximately 23 g/kg of extract at an estimated cost of manufacturing of US$ 133.16/kg.     

Measurement of entrainer effects of water and ethanol on solubility of caffeine in supercritical carbon dioxide by FT-IR spectroscopy

The solubilities of caffeine in supercritical CO₂, supercritical CO₂ + water, supercritical CO₂ + ethanol, and supercritical CO₂ + water + ethanol were measured with a circulation-type apparatus combined with an on-line Fourier transform infrared (FT-IR) spectrometer at 313.2 K and 15.0 MPa. The solubilities of caffeine were determined with the peak absorbances of caffeine at 1190 cm⁻¹. The solubilities of caffeine increase until water is saturated in supercritical CO₂. The maximum increase rate is 22%. In CO₂ + caffeine + ethanol system, the solubilities of caffeine increase with increasing the concentration of ethanol. The solubility of caffeine becomes five times when 1000 mol m⁻³ of ethanol is added. In CO₂ + caffeine + water + ethanol system, the solubilities of caffeine are smaller than those with single entrainer of water or ethanol. The shape of the peaks of two CO stretching bands for caffeine were changed by the addition of ethanol. It was confirmed that the interaction species of caffeine interacting with ethanol are produced by deconvolution of the CO stretching bands. The enhancement of solubility for caffeine in supercritical CO₂ by the addition of ethanol is due to the hydrogen bonding between caffeine and ethanol.     

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.     

Obtaining phenolic compounds from jatoba (Hymenaea courbaril L.) bark by supercritical fluid extraction

The extraction of polyphenol compounds from jatoba (Hymenaea courbaril L. var stilbocarpa) bark using supercritical fluid extraction (SFE) with CO₂ and cosolvents has been investigated. Among the solvent systems studied, SFE using CO₂ and water (9:1, v/v), at 323 K and 35 MPa, presented the best results, with extract yield of 24%, and with high antioxidant activity (IC₅₀ of 0.2 mg/cm³). This solvent system was used to determine global yield isotherms, which were built at 323 and 333 K, and 15, 25, and 35 MPa, using a second lot of jatoba. The highest yield was 11.5% at 15 MPa and 323 K, with maximum total phenolic compounds (TPC) of 335.00 mg TAE/g extract (d.b.) and total tannins content of 1.8 g/100 g raw material. A kinetic experiment was performed using optimized conditions, yielding 18% extract, and the kinetic parameters were used to scale-up the process from laboratory to pilot scale. Chemical analyses showed high content of phenolic compounds in the extracts of jatoba bark mostly due to the presence of procyanidins.     

Supercritical fluid extracts from tamarillo (Solanum betaceum Sendtn) epicarp and its application as protectors against lipid oxidation of cooked beef meat

The possibility of using the tamarillo (Solanum betaceum (Cav.) Sendtn (syn. Cyphomandra betacea)) epicarp as source of compounds with antioxidant activity in cooked beef meat (CBM) was explored. Extracts from tamarillo by supercritical fluid extraction (SFE) and Soxhlet extraction (SE) were obtained. The SFE was performed using pure CO₂ at different temperatures and pressures (40 and 50 °C; 10, 20 and 30 MPa) and CO₂ added with ethanol (CO₂/EtOH) as co-solvent (2, 5 and 8%, w/w). The SFE kinetics and mathematical modeling of the overall extraction curves (OEC) were also investigated. EtOH and hexane were used in the SE. The antioxidant activity (AA) of extracts was evaluated in CBM as well as the protection against lipid oxidation was determined by measuring lipid hydroperoxides (LHP) and thiobarbituric acid reactive species (TBARS). The extract obtained by SFE with CO₂/EtOH (50 °C/30 MPa and 2% of EtOH) showed the highest AA. In SFE, the co-solvent addition improved considerably the AA and the extraction yield. The extracts obtained by SFE with CO₂/EtOH showed a better AA compared with the synthetic antioxidant TBHQ. The highest yield values were achieved by SE with ethanol (7.7 ± 0.4%) and by SFE with 5% EtOH (1.9 ± 0.1%). The results indicate that extracts of tamarillo epicarp are a potential source of antioxidant compounds.     

Exploiting microalgae as a source of essential fatty acids by supercritical fluid extraction of lipids: Comparison between Scenedesmus obliquus,Chlorella protothecoides and Nannochloropsis salina

Supercritical CO₂ extraction from microalgae is applied with the aim of obtaining an oil rich in α-linolenic (ALA) essential fatty acid and with a low ω6:ω3 ratio. The maximum extraction yield is obtained at 60 °C and 30 MPa with 0.4 kg/h of CO₂ and 5% of co-solvent (ethanol). When the effect of pressure, temperature and density on the supercritical extraction yield and solubility are studied, the thermodynamic cross-over is found at a pressure close to 30 MPa, while the extraction cross-over occurs at around 25 MPa. The experimental solubility data are correlated by literature empirical models. Mathematical models developed by Sovová are applied to describe the experimental extraction curves. Soxhlet extraction of lipids is also carried out, obtaining a similar fatty acids profile but proving to be less selective than SCCO₂ method. Among the three species of microalgae examined, results show that Scenedesmus obliquus oil is richer in ω-3 fatty acids and ALA than Chlorella protothecoides and Nannochloropsis salina lipids. The effect of the extraction parameters on ALA content and the fatty acid profile is also analysed, concluding that the ω-3 percentage is favoured by lower temperatures, lower pressures and shorter extraction times.