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.     

Solubility of fatty acids in supercritical carbon dioxide

The solubilities of lauric, linoleic, myristic, oleic, palmitic and stearic acid in supercritical carbon dioxide (SC-CO₂) at different pressures and temperatures were measured. The solubility values obtained in this work were compared with previously published data, and possible causes for observed discrepancies were discussed. The solubilities of the six fatty acids were modeled by Chrastil’s equation, and estimated model parameters were used to plot the solubility isotherms of fatty acids at 313, 323 and 333°K (40, 50 and 60°C) as a function of SC-CO₂ density. The comparison of solubility isotherms of fatty acids and vegetable oil suggests that separation of fatty acids from triglycerides might be possible by using SC-CO₂ at densities less than 700 kg/m³. From the effect of temperature on fatty-acid and vegetable-oil solubility, it seems that the extraction yield could be increased without sacrificing the selectivity of SC-CO₂ for fatty acids by choosing a higher operating temperature. The data also suggest that fractionation of certain fatty acids might be possible by manipulating the processing conditions. Given the values of the constants, Chrastil’s equation could serve as a guideline for choosing appropriate processing conditions and predicting the effect of pressure and temperature of SC-CO₂ on solute solubility.     

Correlation and estimation of solubilities of fatty acids in supercritical carbon dioxide using solution model approach

In this study, solid solubility data of five fatty acids in supercritical carbon dioxide (CO₂) at different temperatures and pressures are correlated using a two-parameter solution model developed from the regular solution model coupled with the Flory⿿Huggins equation. The developed solution model with fewer parameters yields correlated results comparable to those from commonly used semi-empirical equations. In addition, both parameters in the solution model can be further generalized with the chain length of fatty acids and a new predictive solution model is proposed for solubility prediction. The predictive solution model proposed in this study provides better predicted results and yields average deviation in predicted solubilities of 22.1%. To further apply this solution model to other compounds, solid solubility data of three triglycerides in supercritical CO₂ at 313 K are also correlated. After model simplification and generalization, a new predictive solution model for triglycerides is also proposed, which yields average deviation in predicted solubilities of 29.8%. These results demonstrate that the solution model used in this study is applicable for correlation and prediction of solid solubilities of structure-related compounds in supercritical CO₂.     

Enrichment of omega3 fatty acids from Tyulka oil by supercritical CO2 extraction

BACKGROUND: Supercritical CO₂ enrichment of omega3 essential fatty acids (FAs) from Tyulka oil, using a batch process was investigated. Fractional factorial design was applied to evaluate the effects of the five process parameters: pressure (20.26 to 25.33 MPa); temperature (40 to 50 °C); packing fraction (0.5 to 0.7); modifier fraction (2 to 5%); and dynamic time (15 to 25 min), and their binary interactions on the enrichment of extracted omega3 FAs. By employing experimental design and analysis of variance, the variables were evaluated according to the significance of their effect on the yield of extracted omega3. RESULTS: The experimental results confirmed that pressure and dynamic time were the most important factors affecting enrichment of omega3. The amount of modifier in the feed also showed an increasing effect on the response. The binary interaction effects were investigated, and are discussed in detail. CONCLUSION: Optimum conditions were found at 25.33 MPa, 46.65 °C, packing fraction 0.50, modifier 5% and dynamic time 25 min, improving the enrichment of omega3 FAs up to 2.9 times. Copyright © 2009 Society of Chemical Industry     

超临界二氧化碳萃取枸杞籽油的实验研究与数值模拟

建立了一套超临界流体萃取枸杞籽油的实验流程。以二氧化碳为萃取剂,考察了萃取压力、操作温度、二氧化碳流量及原料颗粒度等因素对枸杞籽油萃取率的影响。确定了较佳的萃取工艺条件:压力30MPa,温度313～318K,枸杞籽颗粒40～50目,二氧化碳流量0.3～0.4m3/h时枸杞籽油萃取率最高,可达15.5%。基于萃取器微分单元和固态颗粒微分单元质量守恒原理,建立了微分方程,利用直线推动力近似理论拟合总传质推动力及平衡吸收常数,化简方程,对部分实验结果进行数值模拟。     

The Influence of Supercritical Carbon Dioxide (SC‐CO2) on Electrolytes and Hydrogenation of Soybean Oil

The electrochemical hydrogenation of soybean oil with supercritical carbon dioxide (SC‐CO₂) has been studied to seek ways for substantial reduction of the trans fatty acids (TFA). The solubility of CO₂ in electrolytes and the conductivity of electrolytes were investigated using a self‐made electrochemical hydrogenation reactor. The optimum hydrogenation parameters were assessed. Both the solubility of CO₂ in electrolytes and the conductivity of electrolytes increased with increasing CO₂ pressure. When the pressure reached a critical point of CO₂, the solubility of CO₂ expressed as a mole fraction was 0.42 in cathode electrolyte and 0.1 in anode electrolyte. At 8 MPa, the conductivity of electrolytes was 1.5 times higher than that at 2 MPa. When the pressure was higher than the critical point of CO₂, the solubility of CO₂ in electrolytes and the conductivity of electrolytes reached a stable value. The optimum condition for electrochemical hydrogenation of soybean oil in SC‐CO₂ were reaction pressure (8 MPa), reaction temperature (48 °C), current (125 mA), agitation speed (300 rpm), and reaction time (8 h). Fatty acid profile, iodine value, and TFA content were evaluated at the optimum parameters. This investigation showed that the electrochemical hydrogenation of soybean oil in SC‐CO₂ was improved. The reaction time was shortened by 4 h, and TFA content was reduced by 35.8% compared to traditional hydrogenation process.     

Solubility of red palm oil in supercritical carbon dioxide: Measurement and modelling

The solubility of red palm oil(RPO) in supercritical carbon dioxide(scCO_2) was determined using a dynamic method at 8.5–25 MPa and, 313.15–333.15 K and at a fixed scCO_2 flow rate of 2.9 g·min~(-1) using a full factorial design. The solubility was determined under low pressures and temperatures as a preliminary study for RPO particle formation using scCO_2. The solubility of RPO was 0.5–11.3 mg·(g CO_2)~(-1) and was significantly affected by the pressure and temperature. RPO solubility increased with pressure and decreased with temperature. The Adachi–Lu model showed the best-fit for RPO solubility data with an average relative deviation of 14% with a high coefficient of determination, R~2 of 0.9667, whereas the Peng–Robinson equation of state thermodynamic model recorded deviations of 17%–30%.     

川芎油在超临界二氧化碳中溶解度的测定与关联

Extraction of the Ligusticum Chuanxiong oil with supercritical CO2 （SC-CO2） was investigated at the temperatures ranging from 55℃ to 70℃ and pressure from 25 MPa to 35 MPa. The mass of Ligusticum Chuanxiong oil extracted increased with pressure at constant temperature. The initial slope of the extraction was considered as the solubility of oil in SC-CO2. Chrastil equation was used to correlate the solubility data of Ligusticum Chuanxiong oil. An improved Chrastil equation was also presented and was employed to correlate the solubility data, The correlation results show that the values of the average absolute relative deviation are 5.94% and 3.33% respectively, indicating the improved version has better correlation accuracy than that of Chrastil equation.     

Study of kinetics of the d-pinitol extraction from carob pods using supercritical CO2

There is a growing interest in the use of d-pinitol (d-3-O-methyl-chiro-inositol) as a food supplement, thus the use of green and efficient process, such as the supercritical fluid extraction (SFE), to isolate d-pinitol from vegetable raw materials is also an interesting area of research and development. The objective of this work was to study the influence of operating conditions on the SFE of d-pinitol from carob pods. The crucial parameters in SFE, like temperature, pressure, CO₂ flow rate and duration of the process, have been studied. Finally, Naik and Barton models have successfully tested in order to fit the experimental extraction curves.     

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.     

超临界CO2萃取分离桔油中的萜烯和含氧化合物

以冷榨柑橘精油为原料,采用GC/MS对柑橘精油原料进行定性及定量分析,确定了柑橘精油中的7种萜烯类化合物成分作为分离考察对象。实验探讨了超临界萃取压力、萃取温度、萃取时间和CO2流量等因素对含氧化合物分离效果的影响。实验结果表明,萃取相中萜烯类化合物的回收率总体上随着萃取压力、温度、时间和CO2流量的增大而增大。当萃取压力为12MPa,萃取温度为45℃,萃取时间为4h以及CO2流量为1.0L/min时,分离效果最佳,其萃取相中萜烯类化合物的回收率高达90.03%。     

Enzymatic epoxidation of soybean oil methyl esters in the presence of free fatty acids

Epoxides of soybean oil methyl esters (SMEs) are biodegradable, non‐toxic, and renewable epoxy plasticizers. The objective of the present work was to investigate the effects of free fatty acids on the enzymatic epoxidation of SMEs. The results showed that the epoxidation of SMEs depended on the type of the added free fatty acid. For saturated (≤C_18:0) and monounsaturated free fatty acids, the epoxy oxygen group content (EOC) of SMEs increased with increasing carbon chain length of free fatty acids; for branched‐chain unsaturated free fatty acids, the EOC of SMEs decreased in the presence of hydroxyl group (OH) and hydroperoxide (OOH) of free fatty acids; the EOC of SMEs decreased with increasing number of double bonds of free fatty acids. The maximum EOC and the initial epoxidization rate (V₀) linearly decreased with increasing peroxide value of SMEs. The highest EOC (6.87 ± 0.3%) of SMEs was obtained using behenic acid as reaction material, which was similar with that of stearic acid (EOC 6.75 ± 0.2%).     

Continuous catalyst-free production of fatty acid ethyl esters from soybean oil in microtube reactor using supercritical carbon dioxide as co-solvent

This work reports the transesterification of soybean oil in supercritical ethanol in a continuous catalyst-free process in microtube reactor using carbon dioxide as co-solvent. For this purpose it was employed two microtube reactors with different internal diameter, 0.775 and 0.571 mm. The experiments were performed in the temperature range of 523-598 K, pressure of 10 MPa and 20 MPa, oil to ethanol molar ratio of 1:20 and 1:40, and co-solvent to substrates mass ratio from 0.05:1 to 0.2:1. Results demonstrated that temperature, pressure and co-solvent to substrate mass ratio had a positive effect on fatty acid ethyl esters (FAEE) production, with appreciable yields achieved at 598 K, 20 MPa, oil to ethanol molar ratio of 1:20, using a CO₂ to substrate mass ratio of 0.2:1. The micro-reactor with the smallest inner diameter led to slightly higher FAEE yields at the specified reactions conditions compared to the micro-reactor with greater internal diameter. A semi-empirical kinetic model was proposed in attempt to represent the experimental data with satisfactory fitting results found.     

Transesterification kinetics of palm olein oil using supercritical methanol

Continuous transesterification of palm olein oil using supercritical methanol was investigated in the absence of a catalyst. The variables studied were reaction temperature (270–350 °C), pressure (20–40 MPa), and residence time (5–25 min), with a methanol-to-oil molar ratio of 40. Preheating at 245 °C was used to form a homogeneous phase in the absence of thermal decomposition of palm olein oil. The activation energies and reaction activation volumes of the fatty acid methyl ester (FAME), and those of the individual components (C16:0, C18:0, C18:1, and C18:2 methyl esters), were calculated. The entropies of activation (ΔS^‡) of the transesterification reactions were also obtained. As the transesterification of vegetable oil in supercritical methanol included a strongly negative (−175 J/mol K) entropy of activation, transesterification required harsh conditions.     

Modeling and optimization of process parameters for supercritical CO2 extraction of Argemone mexicana (L.) seed oil

This research article deals with the determination of optimal conditions of extraction parameters (e.g. temperature (60–100?°C), pressure (200–350?bar), particle size (0.5–1.0?mm), flow rate-CO₂ (5–15?g/min), and the % of co-solvent (0.0–10% of flow rate-CO₂) resulting to the optimal cumulative extraction yield during the supercritical fluid extraction of Argemone mexicana (L.) seed oil with and without a modifier (ethanol) using a supercritical carbon dioxide as solvent. A “five-factors-three-levels” Box-Behnken design under the response surface methodology was used to show independent and interactive effects of extraction parameters. A mathematical regression model was expressed properly by a quadratic second-order polynomial equation. The maximum oil yield (42.86%) from A. mexicana seeds was obtained with the optimal conditions (85?°C, 305?bar, 0.75?mm, 11?g/min, and 9% of flow rate-CO₂) of extraction parameters. The fatty acids analysis of the seed oil was done using gas chromatography and found its suitability as bio-fuel.     

A green separation process for recovery of healthy oil from pumpkin seed

In this study, pumpkin seeds, called as “Ürgüp Sivrisi” and grown in Cappadocia region, were used as plant materials because of high aroma contents. In the supercritical fluid extraction of pumpkin seed oil, the effect of main process parameters as the particle size (250-2360 μm), the volumetric flow rate of supercritical solvent (0.06-0.30 L/h), the operating pressure (20-50 MPa), the operating temperature (40-70 °C), the type of entrainer (ethanol and n-hexane) and those concentrations (0-10 vol.%) on the extraction yield, the oil solubility and the initial extraction rate were investigated. A cross-over effect for the extraction of pumpkin seed oil using supercritical CO₂ was determined at the operating pressure of 20-30 MPa. The maximum extraction yield obtained with entrainer free was reached 0.50 g oil/g dry seed at 600-1180 μm, 0.12 L/h, 50 MPa and 70 °C for the operation time of 5 h. The maximum extraction yield obtained with ethanol as an entrainer in the experiments was reached 0.54 g oil/g dry seed at the conditions of 600-1180 μm, 0.12 L/h, 30 MPa, 40 °C and 8 vol.% for the operating time of 2 h. The oil compositions were determined by gas chromatography analysis and the results showed that the compositions of pumpkin seed oil which were obtained by means of organic solvent extraction and supercritical fluid extraction were similar. The average oil compositions determined as 9.3 (±0.43)% palmitic acid, 7.5 (±0.6)% stearic acid, 32.3 (±0.6)% oleic acid, 48.1 (±0.6)% linoleic acid and 0.7 (±0.3)% linolenic acid. The morphological changes in the seeds were determined by the scanning electron microscopy analysis.     

CO2,H2,N2在MDEA水溶液中的溶解 度

ＣＯ２、Ｈ２、Ｎ２在ＭＤＥＡ水溶液中的溶解度徐国文张成芳钦淑均（华东理工大学无机化工研究所，上海２００２３７）关键词：ＣＯ２Ｈ２Ｎ２溶解度ＭＤＥＡ１前言国外报道的ＣＯ２溶解度数据［１～９］，布点稀疏，无法满足工程计算及动力学研究之需。王挹薇等采...     

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。     

Solubility of fatty acids in subcritical water

A phase equilibrium apparatus was designed to determine the solubilities of stearic acid and palmitic acid in subcritical water at different temperatures and pressures. The dissolution equilibrium time was measured. The effect of an ultrasonic field on dissolution equilibrium was also studied. The results showed that the maximum solubilities of stearic acid and palmitic acid were 0.136 g/100 g and 0.178 g/100 g in subcritical water at temperatures of 180 °C and 160 °C, respectively, and a pressure of 15 MPa for 30 min. An ultrasonic field also clearly promoted the dissolution of fatty acids in subcritical water. The dissolution equilibrium time was shortened to 20 min using ultrasonic oscillation (250 W, 20 kHz).