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.     

Supercritical fluid extraction of walnut kernel oil

The objective of this study was to investigate the effects of the main process parameters on supercritical fluid extraction of walnut (Juglans regia L.) kernel oil. The recovery of walnut kernel oil was performed in a green and high-tech separation process. CO₂ and CO₂ + ethanol mixtures were used as the supercritical solvent. The extraction was carried out at operating pressures of 30, 40 and 50 MPa, operating temperatures of 313, 323 and 333 K, mean particle sizes of 1.78×10⁻⁴, 3.03×10⁻⁴, 4.78×10⁻⁴, 7.00×10⁻⁴ and 9.00×10⁻⁴ m, supercritical CO₂ (SC CO₂) flow rates of 1.67×10⁻⁸, 3.33×10⁻⁸, 6.67×10⁻⁸ and 13.33×10⁻⁸ m³/s and entrainer (ethanol) concentrations of 2, 4, 8 and 12 vol-%. Maximum extraction yield and oil solubility in SC CO₂ obtained at 50 MPa, 333 K, 9.00×10⁻⁴ m, 3.33×10⁻⁴ m³/h were 0.65 kg oil/kg of dry sample and 37.16 g oil/kg CO₂, respectively. The results obtained in this study showed that the crossover pressure effect of walnut kernel oil was at 30 MPa. At 30 MPa and 313 K, the obtained extraction yields above 4 vol-% ethanol reached the organic solvent extraction yield of 68.5 kg oil/kg dry sample. Extraction time was decreased significantly because of the higher solubility of walnut kernel oil in SC CO₂ + ethanol mixtures.     

Supercritical fluid extraction of encapsulated oil products

Standard methods of oil analysis, for example, Soxhlet extraction and supercritical fluid extraction (SFE), were ineffective for recovering oil from encapsulated food products. Efforts were made to enhance SFE of the oil for these products. Samples were hydrated and heated, which helped to break down the encapsulating structure. In addition, extra diatomaceous earth was needed to absorb and disperse the added water. Optimal extraction conditions were established, and quantitative extraction of oil was achieved for various laboratory-prepared and commercially encapsulated food products.     

超临界二氧化碳流体萃取玉米胚芽油

用超临界ＣＯ２流体技术对玉米胚芽油的萃取进行了研究，考察了温度、压力对得油率的影响，初步探讨了分离器的温度、压力以及萃取原料对油品质量的影响。     

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.     

Supercritical CO2 extraction of flaxseed

Extraction of flaxseed oil was performed with supercritical carbon dioxide (SC-CO₂). To investigate the effects of pressure and temperature on the solubility of oil and oil yield, three isobaric (21, 35, and 55 MPa) and two isothermal (50 and 70°C) extraction conditions were selected. Although the maximal solubility of flaxseed oil, 11.3 mg oil/g CO₂, was obtained at 70°C/55 MPa, the oil yield obtained after 3 h of extraction at this condition was only 25% (g oil/g seed×100), which represented 66% of the total available oil of the flaxseed. Lipid composition and FFA and tocol (tocopherol and tocotrienol) contents of the oils obtained by both SC-CO₂ and petroleum ether extraction were determined. The α-linolenic acid content of the SC-CO₂-extracted oil was higher than that obtained by solvent extraction.     

超临界萃取花生中主要成分的研究

采用超临界CO2萃取花生油脂中主要成分,研究了萃取压力、萃取温度、萃取时间和夹带剂用量等对萃取率的影响。结果表明,在CO2流量为10~12 L/h的前提下,最佳工艺条件是:萃取温度45℃,萃取压力30 MPa,萃取时间2.0 h,夹带剂用量20 mL。在此条件下,花生油脂的萃取率可达50.39%。影响提取率的主次因素为萃取压力萃取时间萃取温度夹带剂用量。     

Supercritical fluid extraction to determine the oil content in copra and extracted meal

Supercritical fluid extraction (SFE) was used as a primary method to determine the oil content of copra and its meal. Determination of the oil content of copra takes 9 h, and for meal 6 h are necessary with Soxhlet extraction, whereas SFE determined oil contents in about 10 min. The extremely high oil content of copra makes grinding difficult, as the sample becomes very gummy and it is difficult to remove the entire sample from the grinder. Adding diatomaceous earth to the sample before grinding eliminated the difficulties of cleaning the grinder and also enabled very fast SFE extractions. The variances for Soxhlet and SFE were not significantly different from each other (P>0.10) in both copra and meal oil contents. The 95% confidence interval around the mean differences (SFE-Soxhlet) was (−0.35, 0.90) and (0.08, 0.26) and for copra and meal, respectively. Although the SFE meal oil content (9.81%) was significantly higher than the Soxhlet meal oil content (9.64%), the size of the average difference (0.17%) was relatively small. This small difference was considered acceptable owing to the ability to use SFE in real-time process control. Therefore, SFE can be used to determine the oil content in copra and its meal in less than 10 min.     

Supercritical fluid extraction of oil from millet bran

Proso millet bran [Panicum miliaceum (L.)], variety Dakota White, was extracted with supercritical carbon dioxide (SC-CO₂) to yield crude oil. The effects of operating parameters (pressure, temperature, and specific solvent flow) and of features of the raw material (moisture content and particle size) on oil extraction were investigated. Complete de-oiling of ground millet bran pellets was achieved under 300 bar at 40°C with a specific solvent flow of 2–10 h⁻¹ within 200 to 500 min. Solvent requirements were 20–30 kg CO₂/kg raw material. Composition of crude SC-CO₂ oil extracted under optimal conditions, i.e., fatty acid profile, amount of unsaponifiables, tocopherols, free fatty acids, sterols, sterol esters, waxes, hydrocarbons, and phospholipids, was compared to that of crude oil obtained by petroleum ether extraction. These two oils were similar in terms of fatty acid profile and amount of free fatty acids, unsaponifiables, peroxides, and tocopherols. They differed in respect to phospholipids (present in petroleum etherextracted oil and absent in SC-CO₂ extracted oil), metals, and waxes (lower levels in SC-CO₂ extracted oil). The effects of extraction procedures on oxidative stability of crude SC-CO₂ oil were studied. Ensuring that all pieces of the extractor in contact with the oil were in stainless steel; cleaning the separator, i.e., washing with KOH, rinsing, purging with N₂ and CO₂, and heating; performing a couple of extractions before the main extraction; and achieving the extraction without interruption all positively influenced the oxidative stability of the oil. Conversely, increasing CO₂ purity above 99.5% had no effect. Oxidative stability of the SC-CO₂ oil extracted under these conditions was only slightly lower than that of the oil extracted with petroleum ether.     

Supercritical CO2 extraction of Plumula nelumbinis oil: Experiments and modeling

Supercritical CO₂ extraction of Plumula nelumbinis oil was investigated at temperatures of 308–338 K and pressures of 15–45 MPa. The yield of the extracted oil was 0.128 g/g material at optimal conditions, in which gamma-sitosterol, unsaturated fatty acids and gamma-tocopherol had higher relative concentrations as determined by GC–MS. The broken and intact cell (BIC) model, with reduced adjustable parameters, was utilized to simulate the SFE process. The values of average absolute relative deviation (AARD) were in the range 2.34–10.9%, indicating that the improved method had a similar effect to the BIC model when three parameters were adjusted. The parameters obtained during the modeling had clear physical meanings and were used to gain an in-depth understanding of the SFE process theoretically.     

Supercritical fluid extraction and characterisation of oil from hazelnut

Hazelnut (Corylus avellana L.) oil was extracted with compressed carbon dioxide in the temperature range of 308—321 K and in the pressure range of 18—23.4 MPa. In addition the influence of the superficial velocity, within a tubular extractor was studied. Physical and chemical characteristics of the oil were obtained. The results including contents of free fatty acids, sterols, triacylglycerols and tocopherols were compared with those obtained when n‐hexane was used as solvent. No significant differences were found when the oils extracted by both methods were analysed. The main fatty acid was the oleic acid (83—85%), followed by linoleic acid (6—8%) and palmitic acid (5—6%). The main triglyceride found in hazelnut oils was the trioleylglycerol (OOO) (63.4—69.6%), followed by the linoleyl‐dioleylglycerol (LOO) (11.6—15.5%) and palmitoyl‐dioleylglycerol (POO) (9.9—10.4%). In terms of sterols, the main component was β‐sitos‐terol (∼83%) followed by campesterol (∼6%). The amount of cholesterol was very low (∼0.2%). The CO₂ extracted oil contained about 17% more tocopherols (458.7 μg/g oil) than the oil extracted by n‐hexane (382.8 μg/g). Oxidative stability was studied by using the induction time determined by the Rancimat method. The oil obtained by supercritical fluid extraction (SFE) was slightly more protected against oxidation (8.7 h for SFE extracted oil and 6.7 h for the hazelnut oil extracted with n‐hexane). Both oils presented high stability index values (7.81 for the oil extracted by n‐hexane and 8.7 for the oil extracted with supercritical CO₂). Oil extracted by supercritical CO₂ was clearer than the one extracted by n‐hexane, showing some refining. Besides, the acidity index was 1.6 for the n‐hexane extracted oil and 0.9 for the oil extracted with supercritical carbon dioxide. The central composite non‐factorial design was used to optimise the extraction conditions, using the Statistica, version 5 software (Statsoft). The best results, in terms of recoveries of hazelnut oil by SFE, were found at 22.5 MPa, 308 K and superficial velocity of 6.0 × 10^—4 ms^—1.     

超临界CO2萃取辣椒油的工艺条件优化研究

以三峡库区种植的辣椒为原料,采用超临界CO2萃取技术,从辣椒中提取辣椒油,考察了萃取温度、萃取压力和萃取时间对辣椒油萃取率的影响。结果表明,萃取温度对辣椒油的萃取率影响最大,其次是萃取压力,萃取时间影响最小;超临界CO2萃取辣椒油的最适宜条件为,萃取温度40℃,萃取压力10 MPa,时间75 min,其萃取率为9.37%;超临界CO2萃取技术应用于辣椒油的提取具有工艺简单、操作安全、能耗低、无毒、萃取剂易回收、萃取率和产品纯度高等优点。     

超临界CO_2萃取辣椒油的工艺条件优化研究

以三峡库区种植的辣椒为原料,采用超临界CO2萃取技术,从辣椒中提取辣椒油,考察了萃取温度、萃取压力和萃取时间对辣椒油萃取率的影响。结果表明,萃取温度对辣椒油的萃取率影响最大,其次是萃取压力,萃取时间影响最小;超临界CO2萃取辣椒油的最适宜条件为,萃取温度40℃,萃取压力10 MPa,时间75 min,其萃取率为9.37%;超临界CO2萃取技术应用于辣椒油的提取具有工艺简单、操作安全、能耗低、无毒、萃取剂易回收、萃取率和产品纯度高等优点。     

Supercritical extraction of borage seed oil coupled to conventional solvent extraction of antioxidants

This paper describes the extraction of borage seed oil by supercritical carbon dioxide (SC-CO₂) and the further extraction of antioxidants from the SC-CO₂-defatted borage meal with organic solvents (water, methanol, ethanol and ethyl acetate). The optimal conditions for oil extraction were obtained at 303 and 323 K at 200 bar, 2.5 h and a continuous flow of CO₂ of 1.5 L/h introduced through the bottom when the operating pressure and temperature were reached, attaining a yield of 60%. Borage oil is rich in unsaturated fatty acids; oleic acid, linoleic acid and linolenic acid accounted for 74% of the total fatty acid content under the above conditions. The highest extraction yield was achieved using water or methanol as extracting solvent from the SC-CO₂-defatted borage meal at 303 K and pressures of 200 and 150 bar for water and methanol, respectively. The most potent extracts, according to all methods tested, were obtained with water and methanol.     

Supercritical fluid extraction in sunflower seed technology

Sunflower (Helianthus annuus L.) seed represents an important source for edible oil and its protein fraction is also recognised as valuable for human consumption when suitably purified from polyphenols, which negatively affect colour and nutritional value. On this basis, a main research has been developed, with the aim of testing the technical feasibility of a supercritical fluid extraction (SFE) process involving a preliminary supercritical CO₂ (SC‐CO₂) extraction of oil from sunflower de‐hulled seeds, followed by the removal of polyphenols from de‐fatted meal by means of ethanol coupled with SC‐CO₂. The paper reports the experimental protocol followed, together with the kinetics of the extractions, knowledge of which allows the optimisation of working parameters and the determination of process yields.     

Supercritical fluid extraction of a crude oil, bitumen-derived liquid and bitumen by carbon dioxide and propane

Extractions of a crude oil, a bitumen-derived liquid and bitumen were conducted at several temperatures and pressures with carbon dioxide and propane in order to assess the effect of the size and type of compounds in the feedstocks on the extraction process. The pure-solvent density at the extraction conditions was not the only variable governing extraction, and the proximity of the extraction conditions to the pure-solvent critical temperature affected the extraction yields and the compositions of the extract phases. Higher oil yields were obtained at lower solvent reduced densities when the extraction temperatures were in the vicinity of the pure solvent critical temperature. In the crude oil and native bitumen extractions, as the extraction time and/or the extraction pressure increased, heavier compounds were found in the extract phases. This preferential extraction was not observed with the bitumen-derived liquid. The non-discriminatory extraction behaviour of the bitumen-derived liquid was attributed to its thermal history and to the presence of olefins and significant amounts of aromatics. Phase behaviour calculations using the Peng-Robinson equation of state and component lumping procedures provided reasonable agreement between calculated and experimental results for the crude oil and bitumen extractions, but failed to predict the bitumen-derived liquid extractions.     

超临界CO_2流体萃取植物油的实验研究

建立了一套超临界流体萃取实验装置,就大豆和花生两种植物油超临界流体萃取进行了较为详细的实验研究.在探讨了压力、温度、颗粒度、空隙率以及时间等对萃取率的影响之后,获得了指导实际生产的最佳工艺参数条件.     

Supercritical fluid fractionation of thermally oxidized canola oil

Supercritical fluid extraction procedures were developed to fractionate thermally oxidized canola oil. Canola oil was heated in a sealed glass ampoule for 72 h at 200°C in a forced-convection oven. After heating, the percentages of triacylglycerol (TAG) trimer, dimer, monomer and lowermolecular weight (LMW) compounds in the heated oil sample (as determined by high-performance size-exclusion chromatography) were 3.0, 8.4, 81.3 and 7.3%, respectively. The LMW compounds included diacylglycerols, monoacylglycerols and free fatty acids. Fractions of TAG monomer of approximately 98% purity were isolated after extraction at 408 atm for 45 min. After a second extraction at 442 atm for 45 min, a TAG dimer fraction of 95% purity was isolated. Recoveries of TAG monomer and dimer were 96 and 87%, respectively.     

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.