Influence of operation variables on quality parameters of olive husk oil extracted with CO<Subscript>2</Subscript>: Three-step sequential extraction

Supercritical CO₂ extraction is a viable alternative process for the extraction of high-quality oil from olive husk (also known as olive pomace), a residue obtained in the production of olive oil. We analyzed the effect of pressure (100–300 bar), temperature (40–60°C), solvent flow (1–1.5 L/min), and particle size (0.30–0.55 mm) on four important quality parameters of the oil extracted with CO₂: tocopherol concentration, extinction coefficients at 232 and 270 nm, and saponification value. Response surface methodology was used to obtain mathematical expressions related to the operating variables and parameters studied. Results from these experiments were also used to design a three-step sequential CO₂ extraction procedure to obtain a higher-quality extract. The optimal operational sequence consisted of a first extraction step at 75 bar for 1 h using 1% (vol/vol) ethanol modifier, followed by a second extraction stage at 350 bar for 2.5 h without ethanol and a third step, also at 350 bar, for 2.5 h but using ethanol. These extraction conditions obtained an intermediate fraction of oil with 64% yield and all normal parameters according to European Commission food legislation. This fraction is suitable without any further refining. On the contrary, the oils obtained by hexane extraction and by conventional supercritical CO₂ extraction at optimal conditions are suitable for human consumption after further refining. This last finding may result in improved economics of the sequential CO₂ extraction process compared to the conventional extraction method with hexane.     

Lampante olive oil refining with supercritical carbon dioxide

Lampante olive oil has been treated in a supercritical CO₂ extraction plant operating in a continuous countercurrent mode. We report the results of a systematic investigation to define the optimal operative parameters. We also have examined the compositional variation of lampante olive oil samples with different characteristics and of different geographic origins before and after refining at optimal conditions. Although practical feasibility of the proposed procedure can be questioned, the results demonstrate the possibility of fractionating components contained in the starting oil even if present at trace levels.     

超临界二氧化碳萃取葡萄籽油工艺优化

为了回收利用葡萄酒酿造过程产生的副产品中的有效成分,本文利用超临界CO₂萃取技术从葡萄籽中提取含有不饱和脂肪酸的葡萄籽油,意在考量超临界CO₂技术在萃取葡萄籽油方面的作用。设计单因素实验,研究了萃取压力、萃取温度、CO₂流量以及停留时间对葡萄籽油萃取率的影响。单因素实验结果表明萃取压力对萃取结果的影响最为显著。萃取温度和CO₂流量对萃取率的影响都存在最佳值,当温度和流量超过最佳值,萃取率开始降低。在单因素实验的基础上进行响应面实验,采用中心复合设计进行实验方案设计以优化萃取葡萄籽油工艺。对响应面实验结果进行方差分析,建立多元回归模型,模型P值<0.0001,预测超临界CO₂萃取葡萄籽油的最佳萃取条件为：萃取压力28MPa、萃取温度321 K、CO₂流量15.5L/h,停留时间155min,萃取率达到14.12%。     

Concentration of sterols and tocopherols from olive oil with supercritical carbon dioxide

A process based on the use of a semicontinuous countercurrent supercritical fluid extraction has been developed to isolate and concentrate minor compounds, such as sterols and tocopherols, from olive oil. In the present work, an evaluation of the efficiency of different random packing materials (Raschig rings, Dixon rings, Fenske rings, and glass beads) to selectively separate sterols and tocopherols from olive oil has been performed. Parameters such as recovery, enrichment, and selectivity vs. TG are discussed. Considering the importance of supercritical fluid extraction as a clean processing technology and the interest in minor compounds with nutraceutical properties from olive oil, the process studied represents an alternative to the reuse of low-quality olive oil to extract high added-value products.     

Quality of wheat germ oil extracted by liquid and supercritical carbon dioxide

The extraction of wheat germ oil by liquid and supercritical CO₂ is described from the point of view of both operative method and pretreatment of raw material. The best conditions for wheat germ oil extraction are: pressure, 150 bar; temperature, 40°C; and solvent flow rate, 1.5 L/min at standard temperature and pressure. The yields and fatty acid compositions obtained are very similar to those resulting from the conventional extraction process using hexane as solvent (8.0 wt%), although a higher-quality oil is obtained by using CO₂ as solvent (free fatty acids, 12.4%; tocopherol content, 416.7 mg tocopherol/g wheat germ oil). These factors lead to the conclusion that the extraction process using CO₂ could be economically competitive with the conventional process, since it considerably simplifies the oil refinement stages and completely eliminates the solvent distillation stage, which are the most costly processing steps in terms of energy consumption.     

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.     

Oxidative stability of walnut oils extracted with supercritical carbon dioxide

Supercritical carbon dioxide (SC-CO₂) was used to partially defat walnuts, and the oxidative stability of the extracted walnut oils was assessed. The SC-CO₂-extracted oils were less stable during accelerated storage in the dark than was pressed walnut oil, as determined by PV, headspace analysis by solid-phase microextraction, and sensory methods. The SC-CO₂-extracted oils, however, exhibited greater photo-oxidative stability than did pressed walnut oil by all of these methods, possibly because of the presence of chlorophyll in the pressed oil. Oxidative stability indices and tocopherol contents were significantly lower in the SC-CO₂-extracted oils than in pressed oil.     

Comparison of processes for the supercritical carbon dioxide extraction of oil from soybean seeds

Three different process alternatives for the production of soybean oil by supercritical carbon dioxide extraction were analyzed. The first two processes were organized according to the classical scheme, based on high-pressure extraction followed by separation induced by pressure reduction. Different techniques were used to recover the solvent in these two schemes, in the liquid and in the gas phases, respectively. The third alternative was based on an isobaric scheme—the oil, extracted at high pressure, was separated by chainging the temperature in the separator. In a further improvement, a technique for the heat transfer network integration was added to all the process schemes. The different schemes were used to establish the process configuration that can produce a lower operating cost for soybean oil extraction. Operating costs were considered on an industrial scale to carry out a screening of the different alternatives. The operating cost of these plants were then compared with the hexane extraction process. A substantial reduction in the specific costs was obtained in the case of heat transfer integration, and the operating costs fell in the same range as conventional extraction plants.     

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.     

响应曲面法优化超临界CO2萃取猕猴桃籽油条件

以猕猴桃籽为试验原料,在单因素试验的基础上,采用响应曲面分析法建立了超临界CO2萃取猕猴桃籽油萃取率的二次多元回归方程,探讨了压力、温度、CO2流量等关键因素对萃取率的作用规律。结果表明,萃取压力、温度、CO2流量对萃取率影响显著,萃取压力和温度交互效应影响显著。根据萃取率回归方程对猕猴桃籽油的超临界萃取工艺参数进行了优选,最优工艺参数为:压力31.7 MPa,温度40.2℃,CO2流量27.4 kg/h,该条件下萃取率高达32.57%,与试验值31.24%仅有4.5%的误差,证实了该方程的预测值与试验值之间具有较好的拟合度。超临界CO2萃取的猕猴桃籽油与己烷提取的油脂在脂肪酸组成上没有显著差别。     

Extraction of rice brain oil using supercritical carbon dioxide and propane

Extraction of rice bran lipids was performed using supercritical carbon dioxide (SC−CO₂) and liquid propane. To provide a basis for extraction efficiency, accelerated solvent extraction with hexane was performed at 100°C and 10.34 MPa. Extraction pressure was varied for propane and SC−CO₂ extractions. Also, the role of temperature in SC−CO₂ extraction efficiency was investigated at 45,65, and 85°C. For the SC−CO₂ experiments, extraction efficiencies were proportional to pressure and inversely proportional to temperature, and the maximal yield of oil achieved using SC−CO₂ was 0.222±0.013 kg of oil extracted per kg of rice bran for conditions of 45°C and 35 MPa. The maximal yield achieved with propane was 0.224±0.016 kg of oil per kg of rice bran at 0.76 MPa and ambient temperature. The maximum extraction efficiencies of both SC−CO₂ and propane were found to be significantly different from the hexane extraction baseline yield, which was 0.261±0.005 kg oil extracted per kg of rice bran. A simulated economic analysis was performed on the possibility of using SC−CO₂ and propane extraction technologies to remove oil from rice bran generated in Mississippi. Although the economic analysis was based on the maximal extraction efficiency for each technology, neither process resulted in a positive rate of return on investment.     

超临界CO_2萃取水冬瓜油

研究了用超临界ＣＯ２流体从水冬瓜果实中提取油品的工艺,探索了操作压力、温度、流量及时间对水冬瓜油的萃取率的影响。分析了萃取条件与油品质量的关系,并综合得出了超临界ＣＯ２萃取水冬瓜油的最佳萃取条件。     

Influence of ecological cultivation on virgin olive oil quality

The quality of oil extracted from ecologically cultivated olives of the Picual variety was compared with oil extracted from Picual olives cultivated using conventional methods. Olive trees were grown in a two-section plot. Fruits from each plot were harvested at various stages of ripeness, and acidity value, peroxide index, ultraviolet absorption at 232 and 270 nm, stability to oxidation, sensory analysis, fatty composition, and contents of tocopherols, phenolic compounds, and sterols were determined on oil extracted from each treatment. The results showed that the organic virgin olive oil was of a superior quality to the conventional virgin olive oil in all the quality parameters analyzed.     

Lipase-catalyzed alcoholysis of cod liver oil in supercritical carbon dioxide

Enzymatic alcoholysis of cod liver oil, with an immobilized lipase, was carried out in supercritical carbon dioxide. The enzyme was catalytically active under the experimental conditions used. The reaction medium was investigated to preferentially extract ethyl esters, synthesized during the course of the experiment, from the unconverted cod liver oil substrate and side-products. The effect of pressure changes on the amount of tri-, di-, and monoglycerides and ethyl esters, present in both the extract and the remaining lipid residue, was determined. Furthermore, the fatty acid compositions of the lipid classes were analyzed, and the relative amounts of both eicosapentaenoic acid and docosahexaenoic acid to palmitic acid were determined. The results show that it is possible to preferentially extract the synthesized ethyl esters at low pressures. The extract collected at 9 MPa contained 64 g ethyl esters/100 g extract, while the total amount of all other lipid classes detected was 19 g/100 g extract. As the pressure was increased, the relative amount of the other lipid classes detected in the extract, especially triglycerides, was enhanced. The relative amounts of both eicosapentaenoic acid and docosahexaenoic acid to palmitic acid increased for some lipid classes in the extract. This increase was most pronounced for the monoglyceride lipid class. The integration of biocatalysis and product fractionation, applied in this study, suggests that the potential for biocatalysis in industrial processes is considerably wider than had been thought.     

超临界二氧化碳萃取藿香梗和藿香叶浸膏

藿香不仅是一种中草药,还是一种天然香料植物,可从中提取藿香浸膏和藿香油,用来调配香精,用于日用品和食品的加香。本文通过单因素试验和正交试验,对超临界二氧化碳提取藿香梗和藿香叶浸膏的提取工艺条件进行了优化。超临界二氧化碳萃取藿香梗浸膏的最佳工艺条件是萃取压力15 MPa、萃取温度42 ℃、CO₂流量37 L&#8226;h^-1、萃取时间3.5 h,产率为1.28%;超临界二氧化碳萃取藿香叶浸膏的最佳工艺条件是萃取压力18 MPa、萃取温度39 ℃、CO₂流量37 L&#8226;h^-1、萃取时间3.5 h,产率为2.53%。     

Oxidative stability of sunflower oil extracted with supercritical carbon dioxide

Extraction of oilseeds with supercritical carbon dioxide (SC−CO₂) is a promising technique to obtain vegetable oils. However, instability of such oils has been associated in the past with SC−CO₂ extraction. The reasons underlying such instability were unclear. Results presented here suggest that oil instability may be related to the oxygen content of CO₂. In fact, oil stability decreases sharply when refined oil (additive-free) is re-extracted with SC−CO₂ and can be related to the oxygen content in the CO₂. Never-theless, oil stability could be improved to the level of conventionally extracted oil by adding trace amounts of ascorbic acid.     

Effect of fruit stoning on olive oil quality

Stoning olives has been proposed as an alternative to crushing the whole fruit during the oil extraction process. Seven pairs of oils obtained from stoned and nonstoned olives from five different cultivars were evaluated to determine the effect of the proposed technology on oil quality. The main organoleptic and physicochemical parameters as well as resistance to oxidation showed no obvious influence of stoning on oil quality. Chemometric analysis of the data showed the oils grouped more according to genetics (cultivar) than to technology. Lipoxygenase activity in the paste from whole and stoned olives showed no effect that could be attributed to the technology. Furthermore, the stone did not contribute significantly to increasing the lipoxygenase activity in the olive paste.     

Extraction of essential oil from geranium (Pelargonium graveolens) with supercritical carbon dioxide

This study investigated the supercritical fluid extraction (SFE) of geranium essential oil from geranium (Pelargonium graveolens) using supercritical carbon dioxide solvent. The extraction yield was measured as a function of pressure, temperature and carbon dioxide flow rate. At low pressure (10 MPa) and high temperature (343 K), waxes were co‐extracted with the essential oil, resulting in artificially elevated essential oil extraction yields as no method was available with the SFE apparatus used to separate co‐extracted waxes and oil. At high pressure (30 MPa) and low temperature (313 K), the amount of wax co‐extracted decreased. Under these ‘optimum’ conditions, the extraction yield increased with decrease in flow rate giving a maximum extraction yield of 2.53%. All samples were analyzed by gas chromatography–mass spectrometry and the effect of pressure and extraction time on oil composition was studied. The percentage compositions of terpene hydrocarbons, terpenols, geraniol and geranyl esters were significantly affected by pressure and extraction time. The oil samples obtained by SFE were also compared with commercially obtained steam distilled samples. All major components of the commercially obtained oils were present in the SFE‐obtained oils; however, the percentage composition of the major components differed greatly between steam distilled and SFE oils. Copyright © 2005 Society of Chemical Industry     

Lipase-catalyzed alcoholysis with supercritical carbon dioxide extraction 1: Influence of flow rate

A combined process of lipase (E.C. 3.1.1.3) catalysis and extraction of product with supercritical carbon dioxide was studied. The effect of different flow rates of the extraction fluid on the selective removal of the ethyl esters (EE) synthesized in a lipase-catalyzed alcoholysis of cod liver oil with ethanol was investigated. The faster the flow rate, the faster the extraction rate and the higher the recovery of EE. For example, after a 270-min extraction, the total recovery of EE was 1520 mg for a flow rate of 0.3 liter carbon dioxide at atmospheric pressure and room temperature/min (NL/min) as compared to 250 mg when 0.015 NL/min was used. The concentration of EE in the carbon dioxide was found to decrease with increasing flow rate, which indicates that the rate of diffusion of EE limits their extraction at fast flow rates. A high flow rate was found to result in a more selective extraction of EE, i.e., less amounts of other lipid components present in the reaction mixture were coextracted with the EE. Further, by increasing the flow rate, the equilibrium of the reaction was shifted slightly toward ester synthesis. An increase in the flow rate from 0.015 to 0.075 NL/min resulted in an approximately 10% increase in total conversion (from 73 to 82%), whereas only a negligible increase was obtained when the flow rate was increased further to 0.15 NL/min.