两步扩散模型对超临界CO2萃取丁香油的数值模拟

基于扩散模型方程和集总参数模型方程,首次建立了具有3个可调参数的两步扩散模型方程.该模型同时考虑固体颗粒内扩散阻力与内壁的阻力,能较好地描述超临界流体萃取过程.用两步扩散模型方程模拟了超临界CO<,2>萃取丁香油的动态过程,在实验温度与压力范围内模型计算值与实验数据的平均相对误差AARD在2.33%～19.48%之间,...     

Supercritical fluid extraction from dried banana peel (Musa spp., genomic group AAB): Extraction yield, mathematical modeling, economical analysis and phase equilibria

Supercritical fluid extraction from dried banana peel (Musa spp., subgroup Prata, genomic group AAB, popularly known in Brazil as Enxerto) was studied. The aspects investigated were: overall extraction curve (OEC), mass transfer modeling of the yield curves, economical analysis of the process and phase equilibrium data for the pseudo-ternary system of banana peel extract, carbon dioxide and ethanol. The extraction operating conditions evaluated were: pressure ranging from 100 bar to 300 bar, temperature from 40 to 50 °C and constant solvent flow rate of 5.0 gCO₂/min. Experimental extraction data were correlated using three kinetic models based on mass transfer equations (logistic, diffusion and Esquível models). Phase equilibrium measurements were performed using pressure from 64.9 bar to 239.9 bar and mass fraction of supercritical extract from 0.52 to 3.55 wt%. Yield results ranged from 0.6 to 6.9% d.b. (dry basis). The lowest deviation between experimental and correlated data was obtained by the Logistic model, except for the curve at 300 bar and 40 °C which was best represented by the Esquível model. The economical analysis identified the possibility to apply the supercritical fluids to obtain extracts from banana peel in an industrial scale. Phase equilibrium for the supercritical extract from banana peel with carbon dioxide modified by ethanol exhibited liquid-liquid, vapor-liquid (bubble point) and vapor-liquid-liquid phase transitions. A crossover phenomenon for the systems evaluated was observed for pressures between 200 bar and 240 bar, for both groups of assays, i.e., supercritical extraction and phase equilibrium.     

The analysis of simultaneous clove/oregano and clove/thyme supercritical extraction

The goal of present work was to investigate and explain kinetics and mass transfer phenomena occurring during the SFE from the mixture of two plants with different initial composition. The extractions from pure clove, oregano and thyme as well as from clove/oregano (C/O) and clove/thyme (C/T) mixtures with various initial compositions of plant material were carried out using supercritical CO₂ at 10 MPa and 40 °C. The results indicated that presence of light compounds in supercritical CO₂ originated from the oregano leaves or thyme at the beginning of extraction process increases the extraction rate of compounds from clove bud. Only small added amounts of oregano or thyme to clove bud (C/O - 90:10%, w/w; or C/T - 84:16%, w/w) in the starting plant mixture had the same effect resulted in the similar and the highest increase of the extraction rate and had negligible influence on total extraction yield compared to extract isolated from pure clove. Different mathematical models were used for simulation of experimental data which showed that the highest increase of the solubility of extractable compounds in supercritical CO₂ as well as the highest mass transfer rate in the solid phase during extractions existed during extraction from C/O (90:10, w/w) and C/T (84:16, w/w) mixtures. Decrease of SC CO₂ consumption or shorter time of extraction necessary for achieving desired extract yield in the case of SFE of the clove buds could be important for industrial-scale application.     

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.     

Biodiesel production using supercritical methanol/carbon dioxide mixtures in a continuous reactor

Fatty acid methyl esters (biodiesel) were produced by the transesterification of triglycerides with compressed methanol (critical point at 240 °C and 81 bar) in the presence of solid acids as heterogeneous catalyst (SAC-13). Addition of a co-solvent, supercritical carbon dioxide (critical point at 31 °C and 73 bar), increased the rate of the supercritical alcohols transesterification, making it possible to obtain high biodiesel yields at mild temperature conditions. Experiments were carried out in a fixed bed reactor, and reactions were studied at 150-205 °C, mass flow rate 6-24 ml/min at a pressure of 250 bar. The molar ratio of methanol to oil, and catalyst amount were kept constant (9 g). The reaction temperature and space time were investigated to determine the best way for producing biodiesel. The results obtained show that the observed reaction rate is 20 time faster than conventional biodiesel production processes. The temperature of 200 °C with a reaction time of 2 min were found to be optimal for the maximum (88%) conversion to methyl ester and the free glycerol content was found below the specification limits.     

Phase transition at subcritical and supercritical conditions of triglycerides methanolysis

The analysis of phase equilibrium between methanol and glycerides during methyl esters of fatty acids (FAME or biodiesel) synthesis at high pressure and temperature is very important for describing the kinetic and process design. It was studied at pressure between 1.1 and 28.0 MPa and temperature from 150 to 270 °C. The transition of phases and composition of identified phases was calculated using RK-Aspen EOS and obtained values were also compared to experimentally determined data at subcritical condition (1.1-4.5 MPa and 150-210 °C).Results of experimental investigation, as well as performed simulation of some specified composition of reaction mixture, showed that system of triglycerides and methanol, at the beginning of reaction (at all analysed conditions except for supercritical state of mixture) is in equilibrium between two liquid phases. During the methanolysis of triglycerides, the phase's distribution was changed accordingly and it highly depends on actual composition of reaction mixture, temperature and pressure. Calculated and measured values indicated that distribution of methanol between the oil phase, the methyl esters, and the glycerol rich phase exists and depends of working condition. As a consequence of fact, that the methanolysis of triglycerides (oil) is mainly realized in the oil-rich phase, at the end of reaction, after all triglycerides are converted into FAME and glycerol, the oil phase disappears. Furthermore, according to the results of phase composition calculation, it was shown that from the beginning to the end of reaction one phase only exists, for methanolysis performed at 270 °C and 20.0 MPa.     

Optimization of supercritical carbon dioxide extraction of Passiflora seed oil

This study investigates extraction of Passiflora seed oil by using supercritical carbon dioxide. Artificial neural network (ANN) and response surface methodology (RSM) were applied for modeling and the prediction of the oil extraction yield. Moreover, process optimization were carried out by using both methods to predict the best operating conditions, which resulted in the maximum extraction yield of the Passiflora seed oil. The maximum extraction yield of Passiflora seed oil was estimated by ANN to be 26.55% under the operational conditions of temperature 56.5 °C, pressure 23.3 MPa, and the extraction time 3.72 h; whereas the optimum oil extraction yield was 25.76% applying the operational circumstances of temperature 55.9 °C, pressure 25.8 MPa, and the extraction time 3.95 h by RSM method. In addition, mean-squared-error (MSE) and relative error methods were utilized to compare the predicted values of the oil extraction yield obtained from both models with the experimental data. The results of the comparison reveal the superiority of ANN model compared to RSM model.     

Continuous production of fatty acid methyl esters from corn oil in a supercritical carbon dioxide bioreactor

Continuous production of fatty acid methyl esters (FAMEs) from corn oil was studied in a supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Response surface methodology (RSM) based on central composite rotatable design (CCRD) was employed to investigate and optimize the reaction conditions: pressure (11-35 MPa), temperature (35-63 °C), substrate mole ratio (methanol:corn oil 1-9) and CO₂ flow rate (0.4-3.6 L/min, measured at ambient conditions). Increasing the substrate mole ratio increased the FAME content, whereas increasing pressure decreased the FAME content. Higher conversions were obtained at higher and lower temperatures and CO₂ flow rates compared to moderate temperatures and CO₂ flow rates. The optimal reaction conditions generated from the predictive model for the maximum FAME content were 19.4 MPa, 62.9 °C, 7.03 substrate mole ratio and 0.72 L/min CO₂ flow rate. The optimum predicted FAME content was 98.9% compared to an actual value of 93.3 ± 1.1% (w/w). The SC-CO₂ bioreactor packed with immobilized lipase shows great potential for biodiesel production.     

Optimization of some parameters on agglomeration performance of Zonguldak bituminous coal by oil agglomeration

In this study, the optimization of some parameters on agglomeration performance of Zonguldak bituminous coal by oil agglomeration was discussed. A three-level Box-Behnken design combining with a response surface methodology (RSM) and quadratic programming (QP) were employed for modeling and optimization some operations parameters on oil agglomeration performance. The relationship between the responses, i.e., grade and recovery, and four process parameters, i.e., amount of oil, agitation time, agitation rate and solid content were presented as empirical model equations for both grade and recovery on oil agglomeration. The model equations were then optimized individually using the quadratic programming method to maximize both for grade and recovery within the experimental range studied. The optimum conditions were found to be 14.61% for amount of oil, 8.94 min for agitation time, 1554 rpm for agitation rate and 5% for solid content to achieve the maximum grade. The maximum model prediction of 0.650 grade at these optimum conditions is higher than any value obtained in the initial tests conducted. Similarly, the conditions for maximum recovery were found to be 20.60% for amount of oil, 5 min for agitation time, 1800 rpm for agitation rate and 19.48% for solid content with a prediction of 96.90% recovery, which is also higher than any other recovery obtained in the initial tests conducted.     

Hydrothermal reforming of bio-diesel plant waste: Products distribution and characterization

A viscous waste derived from a bio-diesel production plant, in the form of crude glycerol, was reacted under subcritical and supercritical water conditions and the product composition determined in relation to process conditions. Preliminary analysis of the original sample showed that the main constituent organic compounds were methanol (20.8 wt.%), glycerol (42.3 wt.%) and fatty acid methyl esters (33.1 wt.%). Uncatalyzed reforming experiments were carried out in a 75 ml Hastelloy-C batch reactor at temperatures between 300 °C and 450 °C and pressures between 8.5 MPa and 31 MPa. Oil/wax constituted more than 62 wt.% of the reactions products. At 300 °C, the main product was a waxy material containing mainly glycerol and fatty acid methyl esters. As the temperature increased to supercritical water conditions, low viscosity oils were produced and all of the glycerol was reacted. The oils contained mainly saturated and unsaturated fatty acid esters as well as their decomposition products. The gaseous products were carbon dioxide, hydrogen and methane and lower concentrations of carbon monoxide and C₂-C₄ hydrocarbons. No char formation was observed. However, during alkaline gasification with sodium hydroxide at 380 °C, the reaction products included a gaseous effluent containing up to 90% by volume of hydrogen, in addition to oil and significant amount of whitish solid residue (soap). Sodium hydroxide influenced the production of hydrogen via water-gas shift by the removal of carbon dioxide as sodium carbonate, but also decreased oil product possibly through saponification.     

Methylation of wood fatty and resin acids for production of biodiesel

The purpose of the present paper is to evaluate the potentiality of the wood oil of Oriental spruce (Spruce orientalis) for biodiesel production. Two methods have been applied for obtained wood oil with and without solvent such as separation of crude tall oil from sulfate soaps by Kraft pulping process. Production of biodiesel from wood oil follows two steps, first extraction of oil using a solvent (acetone) and then base catalyzed (KOH) or non-catalytic supercritical methanol transesterification. This paper studied the effect of temperature on transesterification of wood oil to find the optimum temperature of maximum biodiesel yield. Transesterification of the wood oils were performed in a 100-mL cylindrical autoclave using supercritical methanol. In a typical run, the autoclave was charged with a given amount of the wood oil (20-25 g) and alcohol (20-50 g) with changed molar ratios at 500, 525, 550 and 575 K. The yield of the biodiesel produced under optimal condition is 96-98%.     

Supercritical carbon dioxide extraction of triglycerides from Jatropha curcas L. seeds

This study examines the effects of pressure, temperature and solvent to solid ratio (SSR) on extraction efficiency of triglycerides from powdered Jatropha seeds by using supercritical carbon dioxide extraction. Supercritical extractions were designed for pressures ranging from 250 to 350 bar, temperatures ranging from 313 to 333 K and SSR values ranging from 65:1 to 125:1. All values were selected using response surface methodology in order to determine their effects on the concentration of triglycerides from the extracted oil. Using 3750 g of carbon dioxide over 5 h, a supercritical carbon dioxide extraction (at 350 bar, 333 K and an SSR value of 125:1) yielded 43.51% oil. The concentration and extraction efficiency (i.e. recovery) of triglycerides in the extract reached 657.1 mg/g and 97.62%, respectively. Changes in pressure presented more effective in increasing the recovery of triglycerides, but both temperature and the SSR value are important in obtaining high concentration of triglycerides from the Jatropha seeds that are useful for biodiesel materials.     

Solubility of Jatropha and Aquilaria oils in supercritical carbon dioxide at elevated pressures

This study investigated experimental equilibrium solubilities of Jatropha curcas and Aquiliaria crassna oils dissolved in supercritical carbon dioxide at temperatures of 318-338 K and pressures of 20, 25, 30, 35 MPa. The highest solubility of J. curcas and A. crassna oil were 29.8 and 28.4 mg L⁻¹, respectively, at 338 K and 35 MPa. The oil solubilities and the concentration of triglycerides both increased with increasing temperature and pressure. Triglyceride molecules surrounded by carbon dioxide molecules may be proposed since solubilities increased with the flux of supercritical carbon dioxide. The solubility of these two oils linearly increased with the density of supercritical carbon dioxide. Experimental data of the oil solubility were successfully correlated by the Chrastil equation.     

Optimization of process variables for essential oil components from Satureja hortensis by supercritical fluid extraction using Box-Behnken experimental design

The oil and extracts of Satureja hortensis cultivated in Iran were extracted using supercritical carbon dioxide and hydrodistillation method. The oil and extracts were analyzed by GC-FID and GC/MS. The compounds were identified according to their retention indices and mass spectra (EI, 70 eV). The effects of various parameters such as pressure, temperature, percent of modifier (methanol) and extraction time, were investigated by a fractional factorial design (2^4-1) to determine the significant parameters and their interactions. The results showed that the pressure, temperature and percent of modifier are significant (p < 0.05), but the extraction time was found to be insignificant. The response surface methodology (RSM), based on Box-Behnken design was employed to obtain the optimum conditions of the significant parameters (pressure, temperature and percent of modifier). The optimal conditions could be obtained at a pressure of 35.0 MPa, temperature of 72.6 °C, and 8.6% (v/v) for methanol. The main extracted components using SFE were γ-Terpinene (35.5%), Thymol (18.2%) and Carvacrol (29.7%).     

Thermal stability of biodiesel in supercritical methanol

Non-catalytic biodiesel production technologies from oils/fats in plants and animals have been developed in our laboratory employing supercritical methanol. Due to conditions in high temperature and high pressure of the supercritical fluid, thermal stability of fatty acid methyl esters and actual biodiesel prepared from various plant oils was studied in supercritical methanol over a range of its condition between 270 °C/17 MPa and 380 °C/56 MPa. In addition, the effect of thermal degradation on cold flow properties was studied. As a result, it was found that all fatty acid methyl esters including poly-unsaturated ones were stable at 270 °C/17 MPa, but at 350 °C/43 MPa, they were partly decomposed to reduce the yield with isomerization from cis-type to trans-type. These behaviors were also observed for actual biodiesel prepared from linseed oil, safflower oil, which are high in poly-unsaturated fatty acids. Cold flow properties of actual biodiesel, however, remained almost unchanged after supercritical methanol exposure at 270 °C/17 MPa and 350 °C/43 MPa. For the latter condition, however, poly-unsaturated fatty acids were sacrificed to be decomposed and reduced in yield. From these results, it was clarified that reaction temperature in supercritical methanol process should be lower than 300 °C, preferably 270 °C with a supercritical pressure higher than 8.09 MPa, in terms of thermal stabilization for high-quality biodiesel production.     

Biodiesel fuel from Jatropha oil via non-catalytic supercritical methanol transesterification

Transesterification of Jatropha oil using supercritical methanol and in absence of a catalyst has been studied under different conditions of temperature (from 512 to 613 K), pressure (from 5.7 to 8.6 MPa) and molar ratio of alcohol to oil (from 10 to 43 mol alcohol per mol oil). The reaction products were analyzed for their content of residual triglycerides, glycerol, monoglycerides, diglycerides, esters and free acids by high performance liquid chromatography (HPLC), thin layer chromatography (TLC) and titration against KOH.The results have revealed that 100% yield of esters can be obtained using super critical methanol within four min only, at a temperature of 593 K and under a pressure of 8.4 MPa pressure. The molar ratio of methanol to oil was 43:1.     

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.     

Extraction of the essential oil of abajeru (Chrysobalanus icaco) using supercritical CO2

Abajeru (Chrysobalanus icaco) is a plant that has hypoglycemic properties and is often used in Brazilian popular medicine. In order to identify the flavoring and hypoglycemic substances present in this plant, this work has an objective for the extraction of the essential oil presented in the leaves of abajeru using the supercritical fluid extraction (SFE). The supercritical solvent used is CO₂, because of its moderate critical temperature and pressure, atoxicity, low cost and volatility. The experiments were conducted using dried leaves in an apparatus containing a high-pressure pump, a stainless steel extractor of 42 mL of volume and a micrometric valve for sampling. Different operational conditions were tested, varying mainly the temperature (313.15-353.15 K) and the pressure (10.5-20 kPa) in order to investigate the efficiency of the process. The results showed that the best operational condition was at 20 kPa and 353.15 K. To compare the supercritical carbon dioxide results, the essential oil was also extracted by hydrodistillation and soxhlet, using ethanol as solvent. The chromatographic analysis showed that the different technologies studied extracted the same classes of compounds but the SFE obtained the extract with potential hypoglycemic activity with the presence of lupenol.     

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 supercritical fluid extraction of Jordanian oil shale utilizing different co-solvents

In this study, extracting shale oil from Jordanian oil shale using supercritical fluid extraction has been investigated. Experimental data indicates that by using supercritical extraction with carbon dioxide, using co-solvents can be viable. A relatively high yield can be obtained at relatively moderate pressure. At the highest temperature and pressure of 450 °C and 3200 psi, respectively, and with hexane as a co-solvent, the highest yield obtained was 100 kg/ton of oil shale, which was at the highest temperature and pressure of 450 °C and 3200 psi, respectively, and with hexane as a co-solvent. Increasing both the operating pressure and temperature increases the oil yield. In the supercritical state, carbon dioxide along with other co-solvents, such as hexane and acetone, interact with the kerogen leading to the dissolution of fragments due to an increase in solubility and mass transfer.Increasing the particle size of oil shale for extraction decreases the oil yield. Most of the extracted oil obtained is saturated hydrocarbons, olefinic and a portion of aromatic hydrocarbons. As the extraction temperature increases, the production of low-molecular weight compounds increases.