Oxidative stability of oils containing olive leaf extracts obtained by pressure,supercritical and solvent‐extraction

The effect of the addition of olive leaf (Olea europaea, cv. Arbequina) extracts, i.e. hydroalcoholic (ethanol–water 1:1; OHE), juice (OJ) and supercritical fluid‐CO₂ (OSFE) on the oxidative stability of vegetable oils with different unsaturation, such as soybean oil (SBO), canola oil (CO) and high oleic sunflower oil (HOSO), were studied at two concentrations (250 and 630 mg/kg oil, expressed as caffeic acid equivalent (CAE)). The extracts were characterized by the total phenolic content (Folin–Ciocalteau method), phenol chromatographic profiles (LC‐MS) and antioxidant activity (DPPH). OHE showed the highest phenol content (7.7 mg CAE/mL) while OJ and OSFE showed values of 5.4 and 2.2 mg CAE/mL, respectively. Oleuropein and its derivatives were the major phenolic compounds identified in OHE. The addition of 630 mg CAE/kg oil of OHE and OSFE to HOSO, SBO and CO showed an antioxidant effect, increasing significantly the induction time (IT) (p<0.05). That effect was highest when the system was more monounsaturated. In contrast, OJ showed a pro‐oxidant effect for all oils systems for both concentration studied. This behaviour could be attributed to the diphenol oxidase (PPO) activity.     

Mass transfer enhancement in supercritical fluid extraction by acoustic waves

A computational fluid dynamics model of extraction of a solute (caffeine) from a porous solid matrix (coffee beans) using a supercritical solvent (carbon dioxide) is developed. Supercritical fluid extraction of a solute from a solid matrix is a slow process even when solute free solvent is circulated. The use of acoustic waves represents a potential efficient way of enhancing mass transfer processes. The effect of acoustically excited flows on supercritical fluid extraction from a porous solid matrix is investigated. The mathematical model considers diffusion-controlled regime in the porous solid matrix and convective-diffusive transport in the bulk fluid. Henry's law is used to describe the equilibrium states of the solid and the fluid phases. Accurate representation of the thermo-physical properties of supercritical solvent is considered by using the NIST Standard Reference Database 12. The conservation equations for mass, momentum, energy and species are numerically solved using implicit finite volume method. The effect of process parameters, such as initial state (pressure and temperature) of solvent and acoustic waves on the yield of solute extraction is also investigated numerically.     

超临界流体萃取固态物料的动力学模型

萃取速率和萃取量是超临界流体萃取过程设计的重要依据。对超临界流体萃取固态物料的动力学模型进行了评述。分析了各种动力学模型所描述的萃取机理和模型的求解方法 ,并对各种模型进行了比较 ,指出了各自的适用范围。     

超临界流体萃取技术的发展现状

超临界流体萃取作为一种新型的分离技术,越来越受到各行业的关注和重视,并已广泛应用于医药、食品、化妆品及香料工业等领域.作者对超临界流体萃取技术进行了评述,主要从超临界CO2流体萃取技术的原理、工业应用及其强化过程等几个方面,介绍了国内外关于超临界流体分离技术的最新研究动态,最后针对超临界萃取技术应用现状,探讨了其目前存在的问题及应用前景.     

植物种子油超临界流体萃取研究进展

论述了植物种子油超临界流体萃取技术的重要性和最新发展 ,重点就植物种子油萃取研究领域内的实验研究、数学建模以及过程控制和模拟优化技术进行了评述。介绍了人工神经网络技术在超临界流体萃取过程动力学研究中的应用     

Supercritical fluid extraction from Priprioca: Extraction yield and mathematical modeling based on phase equilibria between solid and supercritical phases

This study aimed to investigate the supercritical carbon dioxide extraction of Cyperus articulatus L. (Priprioca). Before the experiments were performed, the raw material was cleaned, vacuum packed and maintained at −5 °C. The moisture content of the material was determined using an oven with forced air circulation operating at 105 °C. The material was then ground, and the mean diameter of the resulting particles was determined using a set of standard sieves. Extraction was performed at pressures of 100–300 bar, temperatures of 40–50 °C, and extraction times up to 240 min using supercritical carbon dioxide as the solvent. For each load, approximately 50 g of Priprioca was packed into the extractor. According to the experimental results, the yields of extraction were significantly influenced by pressure and temperature. Additionally, this paper provides a mathematical model of the supercritical extraction of Priprioca. The employed mathematical model was based on the mass conservation law, which included two partial differential equations for the solute concentration in the solid and fluid phases. By applying a novel method, the distribution coefficient of the extract between supercritical fluid and solid phases was obtained using the criterion of equal fugacity at equilibrium. The model-predicted extraction yield was then compared with the corresponding experimental data. Additionally, the reasons for the deviations between the model and the experimental data under certain operational conditions are discussed.     

The supercritical carbon dioxide extraction of polyphenols from Propolis: A central composite design approach

The influence of different parameters on the Supercritical Carbon Dioxide (SCO₂) extraction of Italian Propolis were studied with attention to extraction yield and chemical composition of obtained fractions. Operating parameters of SCO₂ were optimized using central composite design. Analysis by multiple regression indicated that pressure and time have a major linear effect on the extraction yield and extract composition.Propolis SCO₂ extracts present different chemical content compared to the ethanolic extract obtained with ultrasound assisted extraction (UAE). SCO₂ extract can be used to perform further UAE ethanol extraction obtaining a flavonoid containing extract. These findings indicate two possible applications of supercritical carbon dioxide for Propolis extraction, one to obtain lipophilic fractions enriched in specific constituents, the other as pre-treatment of the crude material to facilitate the further extraction with ethanol.     

Mathematical modeling and mass transfer considerations in supercritical fluid extraction of Posidonia oceanica residues

Posidonia oceanica residues were extracted with supercritical CO₂ in order to isolate phenolic compounds. The process was optimized by developing a mathematical model based on mass transfer mechanism consisting of adsorption of supercritical fluid on the solid particles, desorption of solute and convective transfer of solute phase along the column. Henry relation between solute concentrations on the surface of the solid (Cs) and in the solid (q) was approximated in order to describe the adsorption/desorption equilibrium. The model parameters such as solid-liquid film mass transfer coefficient (kf), molecular diffusivity coefficient (D_AB) and axial dispersion (D_ax) were estimated using empirical methods. The linear driving force model was applied to improve the yield of total phenolic acid recovery. The optimum parameters were elicited as 25 MPa, 323.15 K and a co-solvent mass ratio of 20% yielding 34.97 μg per gram of dry feed and the model satisfactorily described the extraction yield which can be used for scale-up purposes.     

Selection of suitable model for different matrices of raw materials used in supercritical fluid extraction process

Supercritical fluid extraction (SFE) process is the sustainable green process for the extraction. Mathematical modeling of SFE process is carried out using mass transfer resistances, which vary with the types of solute. In this paper, the effect of matrices such as leaves, flower concrete, flower bud, herb plant, shrub seed and vegetable matter is studied on extraction yield through different models. These models are solved using COMSOL Multiphysics 5.2 solver and results are validated with that of literature. Experimental data of each type of solute matrix are fitted in various models and best suited model is predicted.     

Scale-up study of supercritical fluid extraction process for clove and sugarcane residue

Many scale-up criteria for supercritical fluid extraction (SFE) can be found in literature. However, the studies are often divergent and inconclusive; therefore, more studies on this field are needed. The objective of the present work was to study the scale-up of SFE process focusing application to Brazilian raw materials. A laboratory scale equipment (290 mL extraction vessel) and a pilot scale equipment (5.15 L extraction vessel) were used to study scale-up of SFE for clove and sugarcane residue. The scale-up criterion adopted consisted in maintaining solvent mass to feed mass ratio constant. The criterion was successfully used for a 15-fold scale-up of overall extraction curves for both raw materials studied; yields in pilot scale were slightly higher than in laboratory scale. The criterion studied allows a rapid and simple scale-up procedure, which can be very useful for the purpose of developing SFE technology at industrial scale in developing countries where such technology is still not available at industrial level.     

Scale-up studies of the supercritical fluid extraction of triterpenic acids from Eucalyptus globulus bark

The supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark is investigated, under the context of biorefinery, aiming at the definition of a pathway for the production of enriched extracts in triterpenic acids (TTAs). Scale-up studies are performed, well supported by modeling and by experiments carried out at lab, intermediate and pilot scales (0.5, 5.0 and 80.0 L, respectively). By acknowledging the significant role played by cosolvent (ethanol) addition on the concentration of TTAs, extraction curves are measured at 200 bar and 40 °C, using two different ethanol contents, 2.5% and 5.0% (wt). Taking into account the results achieved by four distinct models, the intraparticle diffusion is confirmed as the prevailing mass transfer resistance in both conditions. Accordingly, the ratio between CO₂ flow rate and biomass weight is adopted as scale-up criterion. Despite the geometric differences between the three units, the measured extraction yields and TTAs concentration evidence good agreement, which validates the established scale-up rule. In the whole, our results legitimate the technical viability of the SFE of E. globulus deciduous bark for future exploitation at larger scales.     

Bioactive extracts of orange (Citrus sinensis L. Osbeck) pomace obtained by SFE and low pressure techniques: Mathematical modeling and extract composition

The objective of this study was to obtain orange (Citrus sinensis L. Osbeck) pomace extract using supercritical fluid extraction (SFE) with CO₂ and with CO₂ and co-solvent. In order to evaluate the high pressure method in terms of process yield, extract composition and biological activity, low pressure methods were also applied to obtain orange extracts, such as ultrasound (UE) and soxhlet (SOX), with different organic solvents, and hydrodistillation (HD). The SFE conditions were temperatures of 313.15 K and 323.15 K and pressures from 100 to 300 bar. The SFE kinetics and mathematical modeling of the overall extraction curves (OEC) were also investigated. The antioxidant potential of the extracts was evaluated by the DPPH method, by the Folin-Ciocalteau method and by the β-carotene/linoleic acid bleaching method. The antimicrobial activity of the extracts was also studied. The main compounds identified were l-limonene, palmitic and oleic acids, n-butyl benzenesulfonamide and β-sitosterol.     

Chamomile extraction with supercritical carbon dioxide: Mathematical modeling and optimization

Supercritical fluid extraction of chamomile using carbon dioxide was investigated in the current study. A model that accounts for both particle and fluid phase was presented for the supercritical extraction. The distribution coefficient of chamomile extract, between solid and solvent has been determined using genetic algorithm method. The model was solved numerically and was successfully validated with experimental data. The model was found to give superior results when compared to experimental data. The effect of particle diameter on extraction yield was investigated using the proposed model. Using genetic algorithm optimization technique 313.15 K and 20 MPa were found as the optimum temperature and pressure, respectively.     

Optimization of supercritical fluid extraction of linseed oil using RSM

The objective of the present study was to develop a supercritical fluid extraction (SFE) method, suitable for extraction of total oil content from linseed, and to be used as a preparative technique for fatty acid determination. Optimum conditions (volume of added ethanol as a co‐solvent, dynamic extraction time (DET), and pressure) were predicted in order to obtain the maximum yield of the extract. Response surface methodology (RSM) and central composite rotatable design (CCRD) were used for modeling the process. Variable values ranged as follows: co‐solvent 0–1 mL, DET 36–60 min, and pressure 45.57–62.05 MPa (6000–9000 psi). Effects of co‐solvent volume and extraction pressure were well described by simplified polynomial equation (R² = 0.85), since DET had no significant influence (p>0.05) on the extract yield. The maximum yield of oil, calculated from experimental results, was obtained with 1 mL of co‐solvent, and pressure of 62.05 MPa. Optimized conditions were used for extraction of oil from four samples of linseed, ground to pass through 1, 2, 3, and 4 mm‐sieve, to determine adequate granulation for SFE. Finally, results for yield and fatty acid composition of the extract obtained using SFE were compared with the results of Soxhlet extraction. Practical applications: The obtained extracts can be used for fatty acid analysis, since they have not been damaged and their fatty acid compositions have not been degraded by reagents or aggressive extraction conditions. It is shown that the selection of appropriate milling equipment for grinding of samples is necessary to achieve adequate granulation and avoid fractionation of sample.     

Black sesame (Sesamum indicum L.) seeds extracts by CO2 supercritical fluid extraction: Isotherms of global yield,kinetics data,total fatty acids,phytosterols and neuroprotective effects

In Brazilian folk medicine, black sesame (Sesamum indicum L.) seeds are one of the most important ingredients present in the tea used to treat stroke victims. Nevertheless, extracts by supercritical extraction of black sesame seeds have not been applied in neuroprotection studies. The objective of this work was to investigate some process variables of supercritical fluid extraction in black sesame to generate extracts applicable in stroke research. Two isothermal (40 and 60 °C) were explored, combined with pressures that ranged from 200 to 400 bar, at a constant mass flow rate of 5.9 × 10⁻⁵ kg/s. The global yields ranged from 37 to 53% in dry basis. The highest mass yield was obtained at 60 °C and 400 bar. The fatty acid composition comprised a high unsaturated/saturated ratio. Chromatographic analysis of phytosterol content in the high global yield extract revealed higher amounts of β-sitosterol + sitostanol, cholesterol, campesterol + campestanol + 24-methylene cholesterol, Δ-5 avenasterol and stigmasterol, while lower levels of Δ-5,24 stigmastadienol, brassicasterol, clerosterol + Δ-5-23 stigmastadienol, Δ-7 avenasterol, eritrodiol and Δ-7 stigmasterol were present in the black sesame extract. Overall extraction curves from the supercritical fluid extraction (SFE) in lower and higher global yields (200 and 400 bar at 60 °C) fitted the Tan and Liou, Goto et al. and Sovová models. These models presented the best residual sum of squares values. Pilot experiments suggest that black sesame extract is neuroprotective following endothelin-1-induced focal ischemia into the motor cortex of adult male rat, observing a decrease in leukocyte infiltration in the group treated with SFE of black sesame seeds when compared with control group.     

超临界流体萃取固态物料数值模拟的研究进展

介绍了超临界流体萃取固态物料的数值模拟方法 ,对固体物料萃取的经验动力学模型、热质类比模型、质量守恒模型的原理及传质特性进行了评述     

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.     

Optimization of Ferulago Angulata oil extraction with supercritical carbon dioxide

In this study, the essential oil of aerial parts of a species of a plant called Ferulago Angulata was extracted by CO₂ to optimize the results of the supercritical extraction process and then the essence was analyzed by the method of GC/MS. This extraction has been performed using Taguchi testing method and choosing L16 array in a laboratorial pilot under the following: pressure (90, 120, 140, and 190 bar), temperature (35, 40, 45, and 55 °C), the average particles size (250, 500, 710, and 2000 μm), flow rate (3, 5, 7, and 12 ml/s) and dynamic time (25, 50, 70, and 120 min). Then optimizing process was done to achieve maximum yield extraction. The optimizing conditions are as follows: 190 bar, 35 °C, 710 μm, 12 ml/s, supercritical flow rate 12 ml/s and the final yield is 0.853%. The total yield of supercritical extraction in the mentioned conditions as well as empirically is 0.97% or about 1%. This is the first report announcing optimization of the operation of supercritical extraction of Ferulago Angulata in a laboratorial condition. In the last report of the same authors, which was also for the first time, the chemical components of this plant essence were identified through supercritical extraction and then were compared with the extraction components of other traditional methods.     

Radical-scavenging activity of extracts from Cordia verbenacea DC obtained by different methods

The possibility of using the leaves of Cordia verbenacea as a new source of natural antioxidant compounds was investigated. In the present work, extracts from C. verbenacea were obtained using different extraction methods: supercritical fluid extraction (SFE), Soxhlet (SE), hydrodistillation and maceration, with the objective to evaluate the methods in terms of yield and antioxidant potential. The high-pressure technique was applied using pure CO₂ and CO₂ with co-solvent at different temperatures and pressures (30, 40 and 50 °C and 100, 200, and 300 bar). Organic solvents with different polarities were used to obtain extracts by low-pressure extraction processes. The extracts were evaluated according to their antioxidant activity using total phenolic content, scavenging abilities on DPPH radical, total antioxidant activities (ABTS^•+), superoxide anion radical-scavenging (O₂^•) and protection against lipid peroxidation in vitro (LPO). Ethyl acetate fraction obtained by maceration and extract isolated by SE using 25% aqueous mixture of ethanol possessed the highest scavenger activity against DPPH radical (IC₅₀ = 9.2 ± 0.4 μg/ml, IC₅₀ = 27.4 ± 0.1 μg/ml, respectively). The SFE with 8% ethanol as a co-solvent produced extracts with distinguished increase in the antioxidant activity. The Soxhlet extract with ethyl acetate exhibited a strong reduction of lipid peroxidation (IC₅₀ = 209 ± 3 μg/ml) value comparable to the standard rutin (IC₅₀ = 203 ± 2 μg/ml). The results indicate that extracts of C. verbenacea have important potential as a source of bioactive compounds with antioxidant activity.     

超临界流体萃取塔的设计

流体相平衡数据是设计超临界流体萃取塔的关键。本文给出了涉及三元混合物相图计量的萃取塔的可行性研究和应用的一些例子。