Supercritical carbon dioxide extraction of oil from Mexican chia seed (Salvia hispanica L.): Characterization and process optimization

Supercritical carbon dioxide (SC-CO₂) was employed to extract oil rich in omega-3 fatty acids (FAs) from chia seeds, and the physicochemical properties of the oil were determined. A central composite rotatable design was used to analyze the impact of temperature (40 °C, 60 °C and 80 °C), pressure (250 bar, 350 bar and 450 bar) and time (60 min, 150 min and 240 min) on oil extraction yield, and a response surface methodology (RSM) was applied. The extraction time and pressure had the greatest effects on oil. The highest oil yield was 92.8% after 300 min of extraction time at 450 bar. The FA composition varied depending on operating conditions but had a high content of α-linolenic acid (44.4-63.4%) and linoleic acid (19.6-35.0%). The rheological evaluation of the oils indicated a Newtonian behavior. The viscosity of the oil decreased with the increase in temperature following an Arrhenius-type relationship.     

Phenolic compounds and some quality parameters of pumpkin seed oil

Pumpkin seed oil has become a recognized source of phenolic compounds. The main aim of this paper was to evaluate the concentration of phenolic compounds and their extraction from pumpkin seed oil. The total phenolics content (TPC) measured in the pumpkin seed oil samples ranged from 24.71 to 50.93 mg GAE/kg of oil. The individual phenolics were tyrosol, vanillic acid, vanillin, luteolin and sinapic acid. Hexane and acetone were the best solvents for the washing step, and methanol for the elution of the phenolics in the solid‐phase extraction (diol‐SPE), whereas bleaching caused a significant increase in the TPC obtained (24.5–30.7%). Additionally, some other oil characteristics were evaluated. The mean oxidative stability of the oils (OSI) was around 4 h, with 5.43 h for the most stable oil. The maximum antioxidant capacity measured by the reduction of the DPPH radical was 62%, which was comparable to 0.16 mM Trolox equivalent. The color of the oil was expressed by L*a*b* coefficients and its hue and saturation. Whereas all samples had similar lightness, their rates of green, red, yellow and blue color were different. Moreover, TPC correlated negatively with lightness, b* and saturation (–0.49, –0.48, and –0.43), and positively with a* and hue (0.58 and 0.52).     

Mathematical model of supercritical extraction applied to oil seed extraction by CO2+saturated alcohol — I. Desorption model

Supercritical fluid extraction of solutes from solid matrix is represented by the extraction curve, where cumulated extracted oil is plotted versus time. Experimental data obtained in laboratory scale and pilot plant is adjusted with different extraction models; in order to predict extraction curves for full-scale extractors. Sometimes, a shortcut method is useful to adjust experimental data; these correlations are typical in most of engineering processes. In this paper, three shortcut methods are reviewed. First, a model based on flux models considering residence time distribution curves for serially interconnected perfectly mixed tanks and plug flow in series or in parallel with them. It could be used to analyze extractor behavior taking into account bed distribution (preferential ways, dispersion). Second, fast adjusting or ‘t^n’ model considers a differential mass balance where mass transfer coefficient is an ‘nth^’ potential function of time; analytical solution gives an explicit equation. Third, it is presented a linear shortcut method by intervals based on Sovovà model; it predicts considering four extraction periods: delay, rapid extraction, slow extraction and depletion; delay time and solubility are evaluated using the ‘t^n’ model. This model gives a process transfer function (Laplace domain). Supercritical fluid extraction of sunflower seed oil with carbon dioxide was performed in a pilot plant at 30.0 MPa and 40°C, using different amounts of methanol, ethanol, butanol and hexanol as cosolvents. Experimental data are fitted with proposed shortcut methods. Fitting error is less than 5% except in linear shortcut method by intervals which is higher.     

Supercritical CO2 extraction of essential oil from yarrow

Essential oil was extracted from yarrow flowers (Achillea millefolium) with supercritical CO₂ at pressure of 10 MPa and temperatures of 40–60 °C, and its composition and yield were compared with those of hydrodistillate. The yield of total extract, measured in dependence on extraction time, was affected by extraction temperature but not by particle size of ground flowers. CO₂-extraction of cuticular waxes was lowest at 60 °C. Major essential oil components were camphor (26.4% in extract, 38.4% in distillate), 1,8-cineole (9.6% in extract, 16.2% in distillate), bornyl acetate (16.7% in extract, 4.3% in distillate), γ-terpinene (9.0% in extract, 9.4% in distillate), and terpinolene (7.6% in extract, 3.9% in distillate). Compared to hydrodistillation, the yield of monoterpenes was lower due to their incomplete separation from gaseous CO₂ in trap but the yield of less volatile components like monoterpene acetates and sesquiterpenes was higher. Hydrolysis of γ-terpinene and terpinolene, occuring in hydrodistillation, was suppressed in supercritical extraction, particularly at extraction temperature of 40 °C.     

Production of titania nanoparticles by a green process route

The manufacture of heterogeneous catalysts and catalyst supports produces substantial amounts of nitrate containing aqueous effluent. The use of nitrate free precursors and an environmentally friendly process would change the manufacture so that the entire process of catalyst synthesis and use can be considered green. In this work the precipitation of titania acetylacetonate nanoparticles for use as catalytic supports using a supercritical carbon dioxide anti-solvent process was investigated over a range of conditions. The effects of 1) pressure, 2) temperature, 3) solution flowrate, 4) solution concentration of TiO(acac)₂ in methanol, 5) nozzle diameter and 6) CO₂/methanol flow ratio on the mean particle size and morphology were studied. Particle sizes between 27 and 78 nm were obtained and were generally string and branch-like with an amorphous nature. Pressure and temperature had little effect on the mean particle size. A decrease in the velocity of the solution flow rate led to an increase in mean particle size and to particles that exhibited greater interconnectivity. It was also observed that an increase in concentration of TiO(acac)₂ in methanol led to an increase in mean particle size. The process shows promise for the production of catalysts by an environmentally acceptable route.     

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.     

Solubility and kinetics of soybean oil and fatty acids in supercritical CO2

Supercritical CO₂ extraction of soybean oil was investigated. The fatty acid composition was determined using GC. The solubility and kinetic experiments were performed in the pressure range of 100–300 bar and in the temperature range of 313–323 K. The solubility data were correlated using empirical equation proposed by Gordillo et al. Mass transfer model described by Martinez et al. was used to describe the kinetic curves of soybean oil. The main fatty acids of soybean oil were linoleic, oleic, palmitic, stearic and linolenic acid. The improved Gordillo et al. equation was proposed to correct the effect of temperature on the solubility. The new equation was successfully applied for calculating the solubility of fatty acids and soybean oil in supercritical CO₂.     

Frying stability of canola oil in presence of pumpkin seed and olive oils

Frying performance of canola oil (CO) was investigated in the presence of 5, 10, and 15% levels of virgin olive oil (VOO) and pumpkin seed oil (PSO) during frying of potatoes at 180°C. Acid value, carbonyl value, total polar compounds content, and total tocopherols content of the oil samples were determined during the frying process. VOO and PSO addition improved the frying stability of the CO. Frying performance of the CO increased more in the presence of PSO than in the presence of the VOO. The PSO levels higher than 5% exerted pro‐oxidant effects, indicating the necessity of investigation at lower levels. The better antioxidative effect of PSO was attributed to its probably different phenolic composition.     

Supercritical fluid extraction of jojoba oil

Supercritical fluid extraction of jojoba oil from Simmondsia chinensis seeds using CO₂ as the solvent is presented in this study. The effects of process parameters such as pressure and temperature of extraction, particle size of jojoba seeds, flow rate of CO₂, and concentration of entrainer (hexane) on the extraction yield were examined. Increases in the supercritical CO₂ flow rate, temperature, and pressure generally improved the performance. The extraction yield increased as the particle size decreased, indicating the importance of decreasing intraparticle diffusional resistance. The maximum extraction yield obtained was 50.6 wt% with a 0.23-mm particle size and a 2 mL/min CO₂ flow rate at 90°C and 600 bar. Use of an entrainer at a concentration of 5 vol% improved the yield to 52.2 wt% for the same particle size and also enabled the use of relatively lower pressure and temperature, i.e., 300 bar and 70°C.     

Continuous enzymatic production of biodiesel from virgin and waste sunflower oil in supercritical carbon dioxide

A continuous process for biodiesel production in supercritical carbon dioxide was implemented. In the transesterification of virgin sunflower oil with methanol, Lipozyme TL IM led to fatty acid methyl esters yields (FAME) that exceeded 98% at 20 MPa and 40 °C, for a residence time of 20 s and an oil to methanol molar ratio of 1:24. Even for moderate reaction conversions, a fractionation stage based on two separators afforded FAME with >96% purity. Lipozyme TL IM was less efficient with waste cooking sunflower oil. In this case, a combination of Lipozyme TL IM and Novozym 435 afforded FAME yields nearing 99%.     

Modeling and optimization of process parameters for supercritical CO2 extraction of Argemone mexicana (L.) seed oil

This research article deals with the determination of optimal conditions of extraction parameters (e.g. temperature (60–100?°C), pressure (200–350?bar), particle size (0.5–1.0?mm), flow rate-CO₂ (5–15?g/min), and the % of co-solvent (0.0–10% of flow rate-CO₂) resulting to the optimal cumulative extraction yield during the supercritical fluid extraction of Argemone mexicana (L.) seed oil with and without a modifier (ethanol) using a supercritical carbon dioxide as solvent. A “five-factors-three-levels” Box-Behnken design under the response surface methodology was used to show independent and interactive effects of extraction parameters. A mathematical regression model was expressed properly by a quadratic second-order polynomial equation. The maximum oil yield (42.86%) from A. mexicana seeds was obtained with the optimal conditions (85?°C, 305?bar, 0.75?mm, 11?g/min, and 9% of flow rate-CO₂) of extraction parameters. The fatty acids analysis of the seed oil was done using gas chromatography and found its suitability as bio-fuel.     

超临界二氧化碳萃取枸杞籽油的实验研究与数值模拟

建立了一套超临界流体萃取枸杞籽油的实验流程。以二氧化碳为萃取剂,考察了萃取压力、操作温度、二氧化碳流量及原料颗粒度等因素对枸杞籽油萃取率的影响。确定了较佳的萃取工艺条件:压力30MPa,温度313～318K,枸杞籽颗粒40～50目,二氧化碳流量0.3～0.4m3/h时枸杞籽油萃取率最高,可达15.5%。基于萃取器微分单元和固态颗粒微分单元质量守恒原理,建立了微分方程,利用直线推动力近似理论拟合总传质推动力及平衡吸收常数,化简方程,对部分实验结果进行数值模拟。     

Effect of kenaf seed oil from different ways of extraction towards ovarian cancer cells

Kenaf (Hibiscus cannabinus) from the family of Malvaceae is a valuable fibre plant native to India and Africa. Kenaf is composed of various active components including tannins, saponins, polyphenolics, alkaloids, essential oils and steroids. It has been used to treat bruises, bilious conditions, fever and puerperium. Nevertheless, the anti-cancer properties of kenaf seed oil have not yet been investigated. In this study, kenaf seed oils obtained by Sonication, Soxhlet and supercritical carbon dioxide fluid extraction (SFE) with 9 different combinations of pressure (bars) and temperature (°C) (200/40, 200/60, 200/80, 400/40, 400/60, 400/80, 600/40, 600/60 and 600/80) were investigated for the cytotoxicities. All the oils were cytotoxic towards ovarian cancer (CaOV3) and colon cancer (HT29) cell lines in a dose dependent manner as detected by using the MTT assay and trypan blue dye exclusion method. Oil from Sonication was the most cytotoxic towards CaOV3 cell line. Treated cells exhibited characteristics of apoptosis such as chromatin condensation and nuclear fragmentation. In conclusion, kenaf seed oils from the three extractions were cytotoxic towards CaOV3 cell line in a dose-dependent manner possibly via the induction of apoptosis. In considering the safety of the product, SFE technology is a better alternative extraction method that is suitable in kenaf seed oil extraction.     

Polymer melt rheology with high-pressure CO2 using a novel magnetically levitated sphere rheometer

A magnetically levitated sphere rheometer (MLSR) designed to measure viscosity of fluids exposed to high-pressure carbon dioxide has been developed. This device consists of a magnetic sphere submerged inside a test fluid within a high-pressure housing and levitated at a fixed point. The housing is constructed from an optically transparent sapphire tube. The cylindrical tube can be moved vertically to generate a shear flow around the levitated sphere. The difference in magnetic force required to levitate the sphere at rest and under fluid motion can be directly related to fluid viscosity. Rheological properties, specifically zero shear viscosities, of transparent high-pressure materials can be measured to a precision of about 5% and over a wide range of viscosities. In addition, operation at constant pressure, in concentration regimes from a pure polymer to an equilibrated polymer/supercritical fluid solution, and at shear rates over several orders of magnitude is possible, eliminating many of the disadvantages associated with other high-pressure rheometers. Experiments performed at different temperatures with a poly(dimethylsiloxane) melt at atmospheric pressure are compared with data from a commercial Couette rheometer to demonstrate device sensitivity and viability. Measurements of a PDMS melt plasticized by high-pressure CO₂ are performed to illustrate the utility of the new rheometer under high-pressure conditions. Experimental data are obtained at 30 °C, for pressures up to 20.7 MPa and CO₂ concentrations reaching 30 wt%. Viscosity reductions of nearly two orders of magnitude compared with the pure polymer viscosity at atmospheric pressure are observed. Additionally, the effects of pressure on a polymer/CO₂ system are directly investigated taking advantage of the constant pressure operation mode of the MLSR. This allows us, for the first time in experiments of polymers with supercritical fluids, to decouple the effects of CO₂ concentration and pressure in a single device.     

Kinetics and specificity of Lipozyme-catalysed oil hydrolysis in supercritical CO2

Blackcurrant seed oil is rich in linoleic and linolenic acids. Selective enzyme-catalysed oil hydrolysis was studied with aim to obtain different levels of α- and/or γ-linolenic acid in the mixture of liberated fatty acids and in the fraction of di- and monoacylglycerols, making them suitable for special dietary needs. The oil was dissolved in supercritical carbon dioxide flowing through a packed bed reactor (temperature 40 °C, pressure 15–28 MPa, and superficial velocity 0.1–0.7 mm s⁻¹) with Lipozyme^®, a 1,3-specific lipase from Mucor miehei immobilised on a macroporous ion-exchange resin. The enzyme activity was stable as long as water precipitation in the reactor was prevented. The reaction was found to be controlled by both Michaelis–Menten kinetics and mass transfer. The maximum rate of fatty acids liberation per unit amount of enzyme, 2.6 × 10⁻³ mol s⁻¹ kg⁻¹, was achieved at the maximum flow velocity and pressure. Compared to oil, the liberated fatty acids contained more α-linolenic, palmitic and stearic acids, while di- and monoacylglycerols contained increased levels of γ-linolenic and stearidonic acids.     

A study on the extraction of essential oil of Persian black cumin using static supercritical CO2 extraction,and comparison with hydro-distillation extraction method

The essential oil of Persian black cumin was extracted using static supercritical CO₂ technique at different temperatures, extraction times, and number of extractions. The composition of extracted oil was measured by GC-MS analysis and 25 components were identified. It was found that the oil recovery was reduced by increasing the temperature. Maximum recovery was achieved at two-step extraction that was about 49%. Both dissolution rate and solubility limited the oil recovery at the tested extraction conditions. The oxygenate components have less dissolution rate than the terpenes. The application of experimental data for design of an efficient dynamic extraction system was discussed.     

Comparison of two kinds of pumpkin seed oils obtained by supercritical CO2 extraction

The oils from two kinds of pumpkin seeds, black and white ones, were extracted by supercritical CO₂ (SC‐CO₂). The technological variables for SC‐CO₂ extraction were optimized and the resulting oils were analyzed by GC‐MS. As a result, the optimal conditions for SC‐CO₂ extraction were as follows: 25～30 MPa, 45 °C, SC‐CO₂ flow rate of 30～40 kg/h. The main compounds in the resulting oils were 9,12‐octadecadienoic acid, 9‐octadecenoic acid, stearic acid, palmitic acid for both types of pumpkin seeds, however, the black seed oil contains more unsaturated fatty acids (UFA) than the white seed oil. On the other hand, some compounds including heptadecanoic acid (0.27%), tetracosanic acid (0.1%), 9‐dodecaenoic acid (0.45%) and pentadecenoic acid (0.05%) were found in white seed oil but not in black seed oil; while eicosanic acid (0.05%), 11,14‐eicosadienoic acid (0.2%), 11‐octadecenoic acid (0.06%), 7‐hexadecenoic acid (0.02%) and 1,12‐tridecadiene (0.02%) were only found in black seed oil.     

Supercritical fluid extraction of sunflower seed oil with CO2-ethanol mixtures

The effect of ethanol addition to supercritical carbon dioxide (SC-CO₂), up to 20%, on sunflower seed oil extraction over the range of 150 to 350 bars and 42 to 80°C was studied. A nonrecirculating home-made bench-scale system was used as extraction equipment. The oil-SC-CO₂-ethanol mixture was reduced to atmospheric pressure in a test tube, where two phases, oil and ethanol, were obtained and ethanol-saturated CO₂ was liberated to the atmosphere. Results show that sunflower oil solubility in SC-CO₂ greatly increases with addition of ethanol as entrainer over the whole range of pressure and temperature conditions. Some phospholipids are co-extracted at levels directly proportional to the added ethanol. Moreover, a large amount of phospholipids was recovered in the ethanolic phase. Acidity of the extracted oil with ethanol as entrainer was lower than that without alcohol. Part of the free fatty acids was found in the ethanolic phase.     

Effect of various extraction conditions on the phenolic contents of pomegranate seed oil

Pomegranate seeds are byproducts of the pomegranate juice industry. Because of the presence of large amounts of certain pharmaceutical and nutraceutical components in the seeds, a proper extraction method to obtain these components is highly demanded in the food industry. In this study, the effect of different extraction methods on the total phenolic contents of the oil extracted from pomegranate seeds of the Malas variety from Shahreza, Iran, was investigated. Four different extraction methods including normal stirring, Soxhlet, microwave irradiation and ultrasonic irradiation using two types of organic solvents as well as a supercritical fluid extraction (SFE) method using CO₂ as solvent were applied. The different organic solvents of this study did not indicate any significant differences in the total phenolic contents of the extracted oils, but the extracted oils from the various conditions of SFE indicated wide changes in the amount of phenolic compounds (7.8–72.1 mg/g). The total phenolic content of the extracted oil from one of the SFE runs was several times greater than those in the extracted oils using organic solvents.     

Influence of pretreatments for extraction of lipids from yeast by using supercritical carbon dioxide and ethanol as cosolvent

Saccharomyces cerevisiae is one of the most studied and industrially exploited yeast. It is a non-oleaginous yeast whose lipids are mainly phospholipids. In this work, the extraction of yeast lipids by supercritical carbon dioxide (SCCO₂) and ethanol as a co-solvent was studied. In particular our attention was focused on the selectivity toward triglycerides, and in a subsequent extraction of the phospholipids present in the yeast. Indeed CO₂ is a non-polar solvent and is not an efficient solvent for the extraction of phospholipids. However, SCCO₂ can be used to extract neutral lipids, as triglycerides, and the addition of polar co-solvents like ethanol, at different compositions, allows a more efficient extraction of triglycerides, and also an extraction-fractionation of phospholipids. In this work SCCO₂ extractions of a specific membrane complex of S. cerevisiae, obtained from an industrial provider, were carried out at 20 MPa and 40 °C, using ethanol as a co-solvent (9%, w/w). It was shown that different pretreatments are necessary to obtain good extraction yields and have a great impact on the extraction. The kinetic of the extractions were successfully modeled using Sovova's model. From the fitting of the main parameters of the model it was possible to compare the effects of the pretreatments over the yeast material, and to better understand the extraction process. Among the seven tested pretreatments the more appropriate was found to be an acid hydrolysis followed by a methanol maceration.