Kinetics of supercritical carbon dioxide extraction of borage and evening primrose seed oil

In the present work, high‐pressure extraction of borage (Borago officinalis L.) and evening primrose (Oenothera biennis L.) seed oil, containing the valuable γ‐linolenic acid (GLA), has been investigated. Extraction was performed with supercritical carbon dioxide on a semi‐continuous flow apparatus at pressures of 200 and 300 bar, and at temperatures of 40 and 60 °C. A constant flow rate of carbon dioxide in the range from 0.17 to 0.20 kg/h was maintained during extraction. The extraction yields obtained using dense CO₂ were similar to those obtained with conventional extraction using hexane as solvent. The composition of extracted crude oil was determined by GC analysis. The best results were obtained at 300 bar and 40 °C for both seed types extracted, where the quality of oil was highest with regard to GLA content. The evening primrose seed oil extracted with supercritical fluid extraction was particularly rich in unsaturated fatty acids: up to 89.7 wt‐% of total free fatty acids in the oil. The dynamic behavior of the extraction runs was analyzed using two mathematical models for describing the constant rate period and the subsequent falling rate period. Based on the experimental data, external mass transfer coefficients, diffusion coefficients and diffusivity in solid phase were estimated. Results showed good agreement between calculated and experimental data.     

Extraction of pollen lipids by SFE‐CO2 and determination of free fatty acids by HPLC

Rape bee pollen lipids obtained by petrol ether extraction (PEE) or supercritical fluid (carbon dioxide) extraction (SFE) were compared with regard to their free fatty acid (FFA) components. Optimal SFE conditions were selected by carrying out the Taguchi method with an OA9 (3³) matrix design, and are as follows: extraction pressure at 35 MPa, temperature at 45 °C, and dynamic extraction time at 90 min. The lipid yield based on PEE was 7.42 wt‐% and the extracts of the desired analytes based on SFE varied in the range of 3.23–5.58 wt‐% under different conditions. With the optimized procedure, the lipid yield was 6.09 wt‐%. The FFA in the lipids were separated with a pre‐column derivation method and 1‐[2‐(p‐toluenesulfonate) ethyl]‐2‐phenylimidazole [4,5‐f]9,10‐phenanthrene as labeling regent, followed by high‐pressure liquid chromatography (HPLC) with fluorescence detection. HPLC analysis shows that the lipids contain abundant unsaturated fatty acids (UFA) in high to low concentrations as follows: linolenic acid (18:3), oleic acid (18:1), linoleic acid (18:2), nervonic acid (24:1), and lignoceric acid (20:4). The UFA contents in the SFE extracts were higher than those after PEE. The results indicated that SFE under suitable conditions is more selective than conventional PEE with regard to lipid extraction and preservation of their quality.     

Extraction of Fatty Acids from <Emphasis Type="Italic">Boletus edulis</Emphasis> by Subcritical and Supercritical Carbon Dioxide

Mushrooms contain many valuable compounds such as fatty acids, carbohydrates, lycopene, lovastatin, trace elements etc. As they are currently valued for biologically active substances, and as high pressure carbon dioxide fluid extraction has been documented as an effective method for preparing bioactive products from plant materials, subcritical and supercritical carbon dioxide extraction of Boletus edulis mushroom was performed. In the extracts obtained, the fatty acids were determined. Response surface methodology (RSM) was applied to investigate the effect of pressure and extraction time on the extraction yield. The analysis of variance showed that pressure and extraction time had a significant effect on the extraction yield in both investigated process. The interaction between pressure and extraction time had a significant effect only in supercritical extraction process of B. edulis. Higher extraction yields have been obtained by subcritical carbon dioxide, and higher linoleic acid content has been determined in extracts obtained by supercritical carbon dioxide.     

Extraction of pomegranate seed oil using subcritical propane and supercritical carbon dioxide

Extraction of oil from pomegranate seeds as a waste product of the juice industry using supercritical carbon dioxide and subcritical propane was studied in this work. The influence of the main operating conditions of extraction, namely, the temperature and pressure of extraction on the oil extraction yield and the correspondent fatty acid profile were analyzed and reported here. Soxhlet extraction with n-hexane was done for comparison with supercritical extraction resulting in a maximum yield of oil of 22.31 wt %. Supercritical carbon dioxide and subcritical propane extracted up to 58.53% (corresponding to maximum yield of 13.06 wt %) and 76.73% (corresponding to maximum yield of 17.12 wt %) of the total amount of pomegranate seed oil as measured using Soxhlet extraction, respectively. Results indicated that the subcritical propane is a suitable and selective solvent for the extraction of the pomegranate seed oil in function of smaller times and pressures employed compared to carbon dioxide extraction. The fatty acid composition of the extracted oil showed the presence of fatty acids of C₁₆, C₁₈, C₂₀, C₂₂, and C₂₄ carbon chains. Punicic (C_18.3) was the major fatty acids and comprise up to 70% of the total fatty acid content of the extracted oil among all samples. Finally, Lack??s plug flow model as developed by Sovova was applied to both extraction systems and a good agreement with the experimental results was obtained.     

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.     

Extraction and Characterization of Seed Oil from Naturally Grown Chinese Tallow Trees

Seeds were collected from locally and naturally grown Chinese tallow trees (CTT) and characterized for general physical and chemical properties and fatty acid composition of the lipids. The effects of four different solvents (petroleum ether, hexane, diethyl ether, and 95 % ethanol) and two extraction methods (supercritical carbon dioxide (SC-CO₂) and conventional Soxhlet) on the properties of the CTT seed oil, including Chinese vegetable tallow (CVT) and stillingia oil (SO), were also investigated. In general, the yields of CVT and SO did not vary based on solvent for Soxhlet extraction and solvent-free SC-CO₂ extraction, except that the yield of CVT from SC-CO₂ extraction was substantially lower. Nevertheless, the CTT seed oil, extracted by SC-CO₂ displayed better quality than those extracted by Soxhlet extraction in terms of color, residual precipitation, and acid value of the oils. The pretreatment of CTT seed by 3 % aqueous sodium bicarbonate solution likely promoted the hydrolysis of triglyceride and caused the high acid value in the CVT samples. The iodine value at around 180 indicated that the SO is a highly unsaturated drying oil. Palmitic (76 %) and oleic (23 %) are two dominant fatty acids in CVT while linolenic (43 %), linoleic (31 %), and oleic (13 %) are the dominant fatty acids in SO.     

Deacidification of black cumin seed oil by selective supercritical carbon dioxide extraction

The deacidification of high-acidity oils from Black cumin seeds (Nigella sativa) was investigated with supercritical carbon dioxide at two temperatures (40 and 60°C), pressures (15 and 20 MPa) and polarities (pure CO₂ and CO₂/10% MeOH). For pure CO₂ at a relatively low pressure (15 MPa) and relatively high temperature (60°C), the deacidification of a highacidity (37.7 wt% free fatty acid) oil to a low-acidity (7.8 wt% free fatty acid) oil was achieved. The free fatty acids were quantitatively (90 wt%) extracted from the oil and left the majority (77 wt%) of the valuable neutral oils in the seed to be recovered at a later stage by using a higher extraction pressure. By reducing the extraction temperature to 40°C, increasing the extraction pressure to 20 MPa, or increasing the polarity of the supercritical fluid via the addition of a methanol modifier, the selectivity of the extraction was significantly reduced; the amount of neutral oil that co-extracted with the free fatty acids was increased from 23 to 94 wt%.     

Production of phytosterol esters from soybean oil deodorizer distillates

Enzymatic esterification and supercritical fluid extraction was used to produce phytosterol esters from soybean oil deodorizer distillates. The raw material was first subjected to a two‐step enzymatic reaction; the product obtained mainly comprised fatty acid ethyl esters, tocopherols and phytosterol esters, together with minor amounts of squalene, free fatty acids, free sterols and triacylglycerols. The phytosterol esters were then purified from this mixture using supercritical carbon dioxide. Experimental extractions were carried out in an isothermal countercurrent column (without reflux), with pressures ranging from 200 to 280 bar, temperatures of 45–55 °C and solvent‐to‐feed ratios from 15 to 35 kg/kg. Using these extraction conditions, the fatty acid esters were completely extracted and, thus, the fractionation of tocopherols and phytosterol esters was studied. At 250 bar, 55 °C and a solvent‐to‐feed ratio of 35, the phytosterol esters were concentrated in the raffinate up to 82.4 wt‐% with satisfactory yield (72%).     

Supercritical Carbon Dioxide Extraction,Fatty Acid Composition,Oxidative Stability,and Antioxidant Effect of Torreya grandis Seed Oil

Torreya grandis seed oil (TGSO) extraction with supercritical carbon dioxide was explored from the extraction conditions, fatty acid composition, its oxidative stability and antioxidant activity in a bench‐scale apparatus. An L₉(3⁴) orthogonal design was applied to optimize extraction parameters. The results demonstrated that the maximum yield of 94.57 % was obtained at 45 MPa, 4 h and 50 °C. There were 18 kinds of compounds found within TGSO; the predominant ingredient was linoleic acid (42.02 %), followed by oleic acid (32.14 %) and dihomo‐γ‐linolenic acid (9.80 %). The IC₅₀ values for 1,6‐bis(diphenylphosphino) hexane radical (DPPH), hydroxyl radical (HO?) and superoxide radical (O₂^·?) were 5.61, 3.16 and 4.20 mg/mL, respectively.     

Supercritical CO2 extraction of oil from seeds of six grape cultivars: Modeling of mass transfer kinetics and evaluation of lipid profiles and tocol contents

The current study focuses on the recovery of grape seed oil by supercritical CO₂ extraction. Grape seeds from six grape cultivars were extracted in two subsequent harvesting years, and the resulting oils were characterized for the relative amount of: (a) lipid classes; (b) lipid acyl chains; and (c) tocopherols and tocotrienols. Comparative extractions were performed by utilizing n-hexane as solvent and by mechanical pressure. A well-established modeling approach was applied to evaluate the mass transfer parameters affecting the kinetics of supercritical CO₂ extraction: with these parameters, process scale-up can be addressed. The results reported in this study testify the potentiality of grape seed oil as a source of unsaturated fatty acids and tocols. Moreover, they offer a clear picture of the similarities and differences among oils from different grape cultivars and obtained through different extraction techniques.     

The processing of new oilseed crops—An economic evaluation

The economics of pilot- to large-scale processing of the new oilssed cropsCrambe abyssinica, Euphorbia lagascae, andDimorphotheca pluvialis into oil, fatty acids, or esters were estimated. It was found that the processing costs forCrambe seed to oil is in the same range as that for rapeseed (≈0.5 U.S. $/kg). Production of fatty acid esters from vernolic and dimorphecolic acids requires some special downstream processing operations that result in processing costs of about 1 U.S. $/kg ester. Good-qualityDimorphotheca oil is much more difficult to obtain and requires supercritical carbon dioxide extraction. Processing costs can be as high as 4 U.S. $/kg oil.     

Canola oil extracted by supercritical carbon dioxide and a commercial organic solvent

Samples of crushed and cooked canola seeds (Okapy Double Zero) were extracted using supercritical carbon dioxide (SCCO₂) (34.0 MPa and 40.0 °C) and a commercial organic solvent (AW406). Oil solubility was obtained through several stepwise extractions under the conditions of this study, and then three additional extractions were performed to measure fatty acid compositions, iodine values, chlorophyll concentrations and unsaponifiable matter. The yield of SCCO₂ extraction was lower than that after extraction with AW406 solvent, due to the incomplete SCCO₂ extraction process. Fatty acid composition analysis showed that the SCCO₂‐extracted oil was slightly higher in polyunsaturated fatty acids and lower in erucic and behenic acids. However, iodine values and unsaponifiable matter did not indicate significant differences (p >0.05) in the two extracted oils. The chlorophyll concentration of SCCO₂‐extracted oil was lower than that in the AW406 solvent, and as a result, the color of SCCO₂‐extracted oil was lighter.     

Regional distribution in the fatty acids of triacylglycerols and phospholipids within soybean seeds (Glycine max L.)

The fatty acid distribution of triacylglycerols (TAG) and major phospholipids (PL) within soybean seeds (Glycine max L.) was investigated in relation to their tocopherol contents. The lipids extracted from four cultivars were separated by thin‐layer chromatography into seven fractions. Tocopherols were predominantly detected in the axis, followed by cotyledons and seed coat. The major lipid components were TAG and PL, while hydrocarbons, steryl esters, free fatty acids and diacylglycerols (sn‐1,3 and sn‐1,2) were also present in minor proportions. With a few exceptions, the dominant PL components were phosphatidylcholine, followed by phosphatidylethanolamine or phosphatidylinositiol. Significant differences (p <0.05) in fatty acid distribution existed when different soybean cultivars were examined. However, the principal characteristics of the fatty acid distribution in the TAG were evident among four cultivars; unsaturated fatty acids were predominantly concentrated in the sn‐2 position, and saturated fatty acids primarily occupied the sn‐1 or sn‐3 position in the oils of the soybeans.     

Tunisian Pistacia atlantica Desf. Extraction Process: Impact on Chemical and Nutritional Characteristics

Plant materials have been used in different fields such as therapeutics, cosmetics, and energy for ages. Several studies have investigated seeds, whether common or not, in order to ensure a better valuation of natural resources. Among these, Pistacia atlantica Desf. has been the subject of several works on its characterization and valorization. Among the current trends in sustainable development and environmental protection, valorizing natural wild plants via green chemistry has become prevalent. One of these plants, Pistacia atlantica Desf., is a tree that grows in arid and semi-arid areas, notably in Tunisia, and produces seeds rich in oil. In this study extracting the oil from its seeds is tried by three methods (supercritical carbon dioxide (CO₂), pressure, and hexane), and the efficiency of these extraction processes is compared in order to obtain the best yield and maximize its valorization in a variety of industrial fields. The obtained oil is found to be rich in polyunsaturated fatty acids, namely linoleic and oleic acids, with a similar acidic composition among all extraction methods. The tocopherol composition of the oil is determined using high performance liquid chromatography. The total polyphenol content is determined using the Folin-Ciocalteu colorimetric analysis method. The results show that the seed oil of Pistacia atlantica Desf. extracted by supercritical CO₂ gives the highest extraction yield (25%) and the lowest acidity and peroxide values with a high degree of oxidation at 232 and 270 nm. This method also gives the highest content of alpha, gamma, and delta tocopherol as well as total phenolic content compared to the other extraction methods. The composition of chlorophylls and carotenes in the seed oil of Pistacia atlantica Desf. is determined. Besides, the analysis of the sterol composition reveals that β-sitosterol is still prevailing. Among all the tested extracts, the supercritical CO₂ extract demonstrates the best antioxidant performance against the tested radicals. The oil extracted by supercritical carbon dioxide (CO₂) is of a higher quality compared to that extracted by pressure and by hexane. Practical applications : The Pistacia atlantica Desf. oil exhibits interesting physicochemical and biological characteristics. The type of extraction affects the quality of the major and minor components in the seeds. However, the supercritical CO₂ method produces a better oil quality with the presence of antioxidants such as tocopherols and polyphenols. In fact, it is found that the oil extracted by the three methods has an important sterolic profile with the predominance of β-sitosterol. According to the classification of vegetable oils, unsaturated fatty acids of atlas pistachio oil can be categorized as oleo linoleic oil, which enhances its nutritional value. Having these characteristics, the use of this oil can be considered in agrifood products.     

木本油料脂肪酸组成、提纯及其应用研究进展

木本油料是我国传统工业油料,应用领域广泛,可作为优质的食用植物油的来源,也可作为生产生物柴油的原料,并且还被用于饲料添加剂和化妆品行业。木本油料中C12~C18不饱和脂肪酸含量高,易被人体吸收,不同提取技术(压榨法、水酶法、超声波辅助法、浸出法等)对木本油料的脂肪酸组成及含量的影响较小。本文对橡胶籽油、核桃油、椰子油、山苍子核仁油、牡丹籽油、油茶籽油和棕榈油等7种木本油料的资源量、应用情况做了简单介绍,并综述了7种木本油料的脂肪酸组成及其提取纯化技术,重点介绍了木本油料中的中长碳链不饱和脂肪酸的提纯技术,并对提纯后的月桂酸、油酸、亚油酸、亚麻酸的应用进行了综述和展望。     

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 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.     

Reactive extraction of oilseeds with dialkyl carbonates

Using dialkyl carbonates as reagents for lipase‐catalyzed transesterification, the reaction is driven by the evolvement of carbon dioxide as the co‐product and thus no longer an equilibrium reaction. Therefore this transesterification method is faster and quantitative conversions can be obtained. Short‐chain dialkyl carbonates, like other short‐chain esters, are also suitable solvents for seed oil extraction. Thus, extraction and transesterification can be combined in a single reaction. This reaction, called reactive extraction, was carried out in a standard Soxhlet apparatus with rapeseed, linseed and calendula seed as the raw materials and with dimethyl and diethyl carbonate as extraction solvent and transesterification reagent at the same time. Fatty acid methyl esters and ethyl esters respectively were obtained with higher yields than those achieved by conventional two step extraction / transesterification. In the case of linseed fatty acid esters and especially calendula seed fatty acid esters, the iodine values of the products obtained by one‐pot‐two‐step reactive extraction were significantly higher.     

Supercritical CO2 extraction of lipids and astaxanthin from Brazilian redspotted shrimp waste (Farfantepenaeus paulensis)

Brazilian redspotted shrimp (Farfantepenaeus paulensis) waste is an important source of carotenoids such as astaxanthin and lipids with a high ω−3 fatty acids content, mainly docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). In order to establish an efficient and environmental friendly recovery process, the lipids and astaxanthin were extracted from the freeze-dried redspotted shrimp waste (including head, tail and shell) using supercritical carbon dioxide. The effects of the extraction conditions of pressure (200-400 bar) and temperature (40-60 °C) on the global yield (X₀), astaxanthin extraction yield and astaxanthin concentration in the extract were evaluated. It was found that the pressure and temperature showed a very low significant effect on the lipid extraction yield using supercritical CO₂. In comparison with lipid extraction by solvents, maximum efficiency of supercritical fluid extraction achieved 64% of hexane extraction yield. On the other hand, temperature and pressure had significant effects on astaxanthin extraction yield. Thegreatest amount of extract was obtained at 43 °C and 370 bar, with 39% of recovery.     

Comparison of Supercritical Fluid and Hexane Extraction Methods in Extracting Kenaf (<Emphasis Type="Italic">Hibiscus cannabinus</Emphasis>) Seed Oil Lipids

The objective of this study was to investigate and compare fatty acids, tocopherols and sterols of kenaf seed oil extracted by supercritical carbon dioxide and traditional solvent methods. Fatty acids, tocopherols and sterols were determined in the extracted oils as functions of the pressure (400 bar, 600 bar), temperature (40 °C, 80 °C) and CO₂ flow rate (25 g/min) using a 1-L extraction vessel. Gas chromatography was used to characterize fatty acids and sterols of the obtained oils while tocopherols were quantified by HPLC. No differences were found in the fatty acid compositions of the various oil extracts and the main components were found to be linoleic (38%), oleic (35%), palmitic (20%) and stearic acid (3%). Extraction of tocopherols using high pressure (600 bar/40 °C, 600 bar/80 °C) gave higher total tocopherols (88.20 and 85.57 mg/100 g oil, respectively) when compared with hexane extraction which gave yield of 62.38 mg/100 g oil. Extraction of kenaf seed oil using supercritical fluid extraction at high temperature (80 °C) gave higher amounts of sterols when compared with hexane extraction.