Supercritical fluid extraction of lipids from spent coffee grounds

Supercritical fluid extraction of lipids from spent coffee grounds was studied in this work. Extraction experiments were carried out with supercritical carbon dioxide at different pressure and temperature conditions to study the influence of those process parameters on the extraction rate and oil composition. Supercritical carbon dioxide extracted up to 85% of the total amount of oil of spent coffee grounds after 3 h of extraction (corresponding to a maximum yield of 15.4 g_oil/100 g_{dry spent coffee}). The fatty acid composition of the extracted oil showed the presence of fatty acids of C14, C16, C18, and C20 carbon chains. Palmitic (C16:0) and linoleic (C18:2) acids were the major fatty acids and comprise about 35% each of the total fatty acid content of the oil. A soxhlet extraction with n-hexane was done for comparison resulting in a maximum yield of oil of 18.3 g_oil/100 g_{dry spent coffee}. Finally, a diffusional model that takes into account the properties of the substrate, the solute partition between the solid and the supercritical phase, and the mass transfer coefficient and axial dispersion in the fluid phase was applied to this system and a good agreement with experimental results was obtained.     

石油炼制中的超临界流体技术

综述了超临界流体的性质 ,重点介绍了超临界流体技术在石油炼制中的应用     

Supercritical fluid extraction of Prunus persica leaves and utilization possibilities as a source of phenolic compounds

Mediterranean countries contribute highly on world peach production and tonnes of waste leaves are released due to pruning. The aim of this study was to investigate the utilization possibilities of the leaves by supercritical fluid extraction. A statistical design was used to evaluate the effect of temperature (40–80 °C), pressure (150–300 bar) and concentration of ethanol as co-solvent (6–20%) at a flow rate of 15 g/min and for a duration of 60 min. The most effective variables were found as pressure and co-solvent ratio (p < 0.005). Optimum extraction conditions were elicited as 60 °C, 150 bar and 6% co-solvent yielding a total phenol content of 79.92 mg GAE/g extract, EC₅₀ value of 232.20 μg/ml and a radical scavenging activity of 53.25% which was higher than the value obtained by conventional solvent extraction method (32.23%). Consequently, Prunus persica L. leaves were found as a potential phenolic source for industrial applications.     

Supercritical fluid extraction from Syzygium aromaticum buds: Phase equilibrium,mathematical modeling and antimicrobial activity

Clove essential oil is an important product to food industry because it presents a powerful antioxidant and antimicrobial potential enabling its use for the substitution of synthetic commercial products for food preservation. The objective of this paper is to study the extraction kinetics for predicting operational condition to obtain Syzygium aromaticum essential oil using CO₂ as solvent by means of the introduction of thermodynamic approach into the mathematical modeling of the process. Extractions were performed at 9000 kPa/313.15 K, 10,000 kPa/313.15 K, 9000 kPa/323.15 K, and 10,000 kPa/323.15 K and the essential oil yields obtained were 14.17%, 12.32%, 13.11%, and 14.02%, respectively. To calculate the extract solubility in CO₂ supercritical, the Peng–Robinson EoS coupled with three mixing rules (van der Waals 1, van der Waals 2 and Mathias–Klotz–Prausnitz) was used and a mass transfer model was employed to represent the relationship yield versus extraction time. The mathematical modeling of the process using the calculated solubility presented high concordance with experimental data. The volatile extracts were analyzed by GC/MS and the major compounds were eugenol and β-caryophyllene. Also, minimum inhibitory concentration (MIC) of supercritical extracts was determined with respect to Escherichia coli, Staphylococcus aureus and Enterococcus faecalis by microdilution method. All samples inhibited the bacterial growth, being the extract obtained at 313.15 K/9000 kPa the most effective.     

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.     

Experimental and Modeling Investigation of Supercritical Extraction of Mannitol from Olive Leaves

The experimental feasibility of mannitol extraction from olive leaves using supercritical carbon dioxide was investigated. The experimental data indicated that increasing the pressure from 200 to 350 bar and decreasing the temperature from 80 to 40 °C resulted in an enhancement of the extraction yield and reduced the partition coefficient significantly. In addition, increasing the extraction time from 10 to 90 min increased the extraction yield, while further increases up to 180 min did not cause any further change. Ethanol was utilized as an entrainer and the maximum extraction yield was obtained using 20 % of ethanol. Moreover, modeling of the supercritical fluid extraction was carried out with the relevant mass transfer mechanisms involved in the supercritical and solid phases, and the appropriate numerical method of finite difference. The numerical results show that the model with three adjustable parameters is capable of predicting the experimental data very well.     

Supercritical fluid extraction of flavonoids from Maydis stigma and its nitrite-scavenging ability

Supercritical fluid carbon dioxide (SF-CO₂) extraction (SFE) of flavonoids from Maydis stigma and its nitrite-scavenging ability were investigated. The effects of extraction time, particle size and co-solvent composition in terms of water content in ethanol were first optimized. Then, a Box-Behnken design combined with response surface methodology (RSM) was employed to study the effects of three independent variables (temperature, pressure and co-solvent amount) on the extraction yield of flavonoids. A maximal extraction yield of flavonoids of approximately 4.24 mg/g of M. stigma by SFE was obtained under optimal conditions (a temperature of 50.88 °C, a pressure of 41.80 MPa, a co-solvent amount of 2.488 mL/g and an extraction time of 120 min with 0.4-mm particle sizes and 20% aqueous ethanol as the co-solvent). Furthermore, the nitrite-scavenging ability of the flavonoid-enriched SFE extracts was assessed using the Griess reagent. The flavonoid-enriched SFE extracts exhibited the highest scavenging ability on nitrite (88.1 ± 3.04%) at the concentration of 500 μg/mL and at pH 3.0. The nitrite-scavenging ability of the extracts appeared to be concentration dependent but negatively correlated with the pH.     

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.     

Supercritical fluid extraction of vegetable matrices: Applications,trends and future perspectives of a convincing green technology

Along more than a decade, R&D on supercritical fluid extraction (SFE) of vegetable matrices has been increasingly reported in the literature. Aiming at portraying the current state of this field and its evolution in terms of raw materials, products, modes of operation, optimization, modeling techniques, and closeness to industrial application, a large compilation of almost 600 essays from 2000 to 2013 has been deeply analyzed in order to unveil those indicators and their trends. Furthermore, strengths and weaknesses are identified, and some remarks that may drive upcoming research are provided.Globally, more than 300 species are reported in the literature, with prevalence of the extraction of seeds (28% of works) and leaves (17%). The main families of extracted compounds, cosolvents and operating conditions adopted are critically examined, being possible to conclude that researchers investigate many times working regions far from the optimum due to practical limitations or absence of experimental optimization. Current phenomenological, statistical and semi-empirical approaches are reviewed, along with scale-up studies, and economic analysis. In the whole, the most comprehensive picture over SFE of vegetable matrices is provided in this review, highlighting pertinent aspects and opportunities that may further consolidate the convincing route of this technology for the next years.     

Supercritical fluid extraction and convergence chromatographic determination of parthenolide in Tanacetum parthenium L.: Experimental design,modeling and optimization

Feverfew (Tanacetum parthenium L., Asteraceae) is a perennial medicinal plant which has been used to alleviate the symptoms of migraines, headaches and rheumatoid arthritis. The herb contains various potentially active constituents such as sesquiterpene-γ-lactones, flavonoids and volatile oil. The main sesquiterpene-lactone in feverfew is parthenolide which is considered to be responsible for the therapeutical effects. Supercritical CO₂ extraction was carried out at different pressures (10–30 MPa), temperatures (40–80 °C) and co-solvent contents (0–10% ethanol) in order to study the extraction yield and the parthenolide recovery of the extracts. Leaves collected before and during flowering and flower heads were investigated. A factorial experiment using a full 3³ design was followed during the experiments and response surface methodology was implemented to analyze the influence of the variables and optimize the extraction. The critical values of parthenolide content were found to be 7% EtOH, 22 MPa and 64 °C in case of all three samples. It was determined, that the optimal conditions of the extraction, where the maximum parthenolide content and extract yield can be reached, do not coincide. The highest yield of parthenolide was obtained in the flower heads (0.604 wt.%).     

Supercritical fluid extraction of lycopene from tomato juice and characterization of its antioxidation activity

A new method to extract lycopene from tomato juice using supercritical CO₂ as solvent and without the need to dry the raw material is presented. To conduct the extraction, the tomato juice was subjected to cycles of centrifugation followed by rinsing with absolute ethanol to partially remove the water present in the solid part of the juice. The influence of the temperature and pressure on the extraction efficiency and on the extract antioxidant activity was studied using a factorial experimental design. The extraction efficiency varied from 7.7% to 76.7% and only extraction temperature had a statically significant effect on the process. The reversed phase HPLC analysis showed that lycopene is the major compound of the extract. The extract that presented higher antioxidant activity was obtained at 40 °C and 350 bar with 12.7 mmol L⁻¹ Trolox/g of extract using the DPPH radical scavenging method and 61.3 mmol L⁻¹ Trolox/g of extract using the rubrene singlet oxygen quenching method.     

Supercritical fluid extraction of peach (Prunus persica) almond oil: Kinetics, mathematical modeling and scale-up

Peach almonds contain oil with important therapeutic and nutritional properties due to the presence of unsaturated fatty acids, high content of oleic acid and other substances. In this study, peach almond oil was obtained by means of supercritical fluid extraction (SFE), with yield up to 24% w/w. The objective of this work was to evaluate the effect of the operation variables in the process kinetics in order to define scale-up parameters, like extractor volume and solvent flow rate. In spite of the importance for industrial application, the definition of a scale-up methodology is difficult. Therefore, the main goal of this work was to study the kinetic aspects of the SFE by modeling the extraction curves and, with these results, suggests a scale-up methodology. The parameters evaluated were extraction pressure, CO₂ flow rate and particle size. The mass transfer models used to describe the extraction curves were logistic model, diffusion model and Sovová model. Four scale-up methodologies, based on mass transfer mechanisms, were applied. The results indicate the best curve fitting by means of Sovová’s model, while the best scale-up criterion was maintaining the ratio Q_CO2/M (solvent flow rate/raw material mass) constant. This study also indicated the convection as the dominant mass transfer mechanism, while the diffusion was the limiting factor. Moreover, the SFE of peach almond oil could be predicted by the scale-up method used.     

超临界流体在环境保护中的应用和展望

超临界流体技术广泛应用于化工、医药、生物、食品、陶瓷等领域。将超临界流体技术用于环境保护则是一个新的研究方向,由于该技术对废物处理具有经济、快速、高效等特点,近几年来发展异常迅速。综述了超临界流体的特性以及超临界流体技术（超临界萃取、超临界色谱和超临界水氧化）在环境保护方面的应用现状。     

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.     

Supercritical fluid extraction of wormwood (Artemisia absinthium L.)

The objective of the work was to optimize the extraction of wormwood oil by supercritical fluid extraction (SFE) of growth-controlled plant material. Different extraction conditions, two growth techniques and various crops were tested and the evolution of the extracted oil composition was screened chromatographically. A comparison with conventional techniques such as hydrodistillation (HD) or organic solvent extraction (OSE) was also presented. Particularly, six CO₂ densities ranging from 285.0 kg/m³ to 819.5 kg/m³ were studied in the range of 9.0-18.0 MPa and 40-50 °C. A systematic study was carried out with plant material from 2005, while SFE of 2006, 2008 and aeroponically grown crops was performed for comparative purposes. The effect of ethanol as a modifier of the supercritical fluid extraction was also studied. The major compounds found in the SFE extracts as well as in the HD essential oils were Z-epoxyocimene, chrysanthenol and chrysanthenyl acetate. A model based on mass transfer equations, the Sovová model, was successfully applied to correlate the experimental data.     

Supercritical extraction of Hypericum caprifoliatum using carbon dioxide and ethanol + water as co-solvent

Hypericum caprifoliatum is a natural source of phloroglucinol derivatives such as hyperbrasilol B, uliginosin B and japonicin A, compounds with pharmaceutical interest due to principally their antidepressant properties. This work studies supercritical fluid extraction to obtain non-volatile compounds from the aerial parts of H. caprifoliatum as well as the influence of the co-solvent as agent of process intensification. The experimental procedures were carried out in a pilot unity. The mathematical simulation of the experimental data was performed by mean of three mathematical models aiming to promote the improvement of the knowledge about this technology. The feasibility of the mathematical model was investigated by mean of fitting of the experimental data obtained. The co-solvents tested were ethanol, water, and water–ethanol mixtures.     

Supercritical fluid extraction and chromatography of emulsifiers

Selected emulsifiers, which included acetylated monoglycerides, lactylated monoglycerides, hexaglycerol distearate, triglycerol mono/dioleate and decaglycerol decaoleate, were separated with capillary supercritical fluid chromatography on a 25% cyanopropyl stationary phase with a mobile phase of CO₂ at 100–150°C. In general, the density/pressure programs that produced the best separations were those with reduced pressure/density ramp rates, which encompassed the largest possible pressure or density range. Samples of acetylated monoglycerides were placed in a supercritical fluid extraction cell on a glass bead bed and extracted for 15 min at 50°C at 340, 408, 544 and 680 atm with CO₂. At 544 atm, 103.6 ± 1.0% of the emulsifiers was extracted. Acetylated monoglycerides were added during twin-screw extrusion of cornstarch (3% w/w emulsifier/corn starch). The acetylated monoglycerides were extracted from the cornstarch extrudate for 15 and 45 min, at 544 and 646 atm and 50–120°C with 0 and 5% added methanol. The percent acetylated monoglyceride extracted after 45 min at 120°C and 646 atm was 60.0 ± 5.7%, while the amount extracted during a 7.5-h Soxtec extraction ranged from 17.9 to 29.4%, depending upon the solvent used.     

Supercritical fluid extraction of lipids from deep-fried food products

A supercritical fluid extraction (SFE) method is described for extracting lipids from fried-food samples. Response surface analysis was used to study the effects of variables, including pressure, temperature, flow rate, and modifier (methanol) on lipid extraction by SFE. The analysis of variance for the response variables indicated that the models developed were satisfactory with coefficients of determination of 0.95 and 0.92 for chicken nuggets and potato fries, respectively. The models predicted that increasing the pressure increased the percentage lipid extracted for both chicken nuggets and potato fries. In addition, the pressure by temperature interactions were significant for chicken nuggets and potato fries. Slight differences in fatty acid composition were observed between SFE and the Goldfisch method. The SF extracts contained traces of C_12:0, C_20:0, and C_24:0 in chicken nuggets and C_14:1, C_18:3, C_22:0, and C_23:0 in potato fries, respectively, which are not found in the Goldfisch extracts. The optimal conditions for extraction are: 53 MPa, 150°C, 4 mL/min, and 10% modifier for chicken nuggets and 53 MPa, 150°C, 3 mL/min, and 0% modifier for potato fries. To duplicate the results of exhaustive Goldfisch extraction with petroleum ether, SFE conditions of 44 MPa, 80°C, 3 mL/min, and 0% modifier were used to produce similar results for both chicken nuggets and potato fries.