超临界CO2萃取的研究与应用

介绍了超临界流体的特性及其萃取的基本原则,讨论了超临界流体萃取技术的优点,评述了超临界CO2的特点,概述了国内外超临界CO2萃取技术在医药,食品,香料,石油化工以及环境保护等领域的开发及应用。     

超临界CO_2萃取大豆油的实验研究

采用超临界CO2 萃取技术进行了大豆油的萃取实验。在压力为 2 0～ 30MPa、温度为 30 8～ 32 3K的范围内 ,考察了萃取压力、萃取温度、流体流量和物料预处理方式等条件对出油率的影响。在本文实验范围内 ,大豆油的最佳萃取工艺条件为 :压力 30MPa ,温度 313K ,物料状态为约 0 .4mm厚的大豆片。流体流量只影响萃取速率 ,而不影响最终的出油率     

Swelling of plant material in supercritical carbon dioxide

Swelling of plant material belonging to several plant families and the influence of swelling on supercritical fluid extraction process were investigated in this study. While swelling of Lamiaceae family species as well as hop cones and pellets occurred during the exposure of plant material to supercritical carbon dioxide, swelling of valerian root and ginger rhizome happened after the decompression step. Optimal pretreatment of herbaceous matrix which will enable commencement of continuous extraction from already swollen plant material was defined on the basis of swelling test results. Experimental results were modeled and energy savings due to the optimal processing on the laboratory scale were calculated. Sorption of carbon dioxide into the hop pellet was measured and the diffusion coefficient in the solid phase was determined. Obtained results indicated that the effective diffusion coefficient in the hop pellet was increased by one order of magnitude due to swelling.     

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.     

Supercritical carbon dioxide extraction of sesquiterpenes from valerian root

Supercritical carbon dioxide extraction of sesquiterpenes from valerian root was investigated. Extractions from cultivar Arterner züctung and two wild grown valerian subspecies were performed. The influence of extraction conditions on extraction yield and chemical composition of obtained extracts was investigated at temperatures from 40 °C to 50 °C and pressures from 10 MPa to 20 MPa. Chemical composition of obtained extracts was analyzed by GC/FID and GC/MS methods. The influence of particle size on extraction process was investigated at 40 °C and 10 MPa. The major constituents of supercritical extracts were valerianol, valerenal, bornyl acetate and kessanyl acetate. Optimal extraction conditions for the cyclopentanoid sesquiterepenes isolation, referred to the content of cyclopentanoid sesquiterpenes in extract, were found to be 50 °C and 15 MPa. Extract obtained from the cultivar was characterized by the higher content of cyclopentanoid sesquiterpenes, as well as valerenal comparing to extracts from wild grown species. At 40 °C and 20 MPa 19.6% of cyclopentanoid sequiterpenes isolated with methanol can be extracted. At 40 °C and 10 MPa, 17.4% of cyclopentanoid sequiterpenes isolated with methanol can be extracted. However, the extract obtained with methanol was characterized by the high content (42.51%) of unwanted isovaleric as well as by the lower content of cyclopentanoid sequiterpenes than the extracts obtained with supercritical carbon dioxide. The process of supercritical extraction was influenced by particle size. In order to simulate the process, mathematical model on the secretory structure scale was derived. Results of the model showed good agreement with the experimental data.     

二氧化碳超临界萃取乙基香兰素粗制品的研究

采用二氧化碳超临界萃取乙基香兰素粗品,研究萃取压力、萃取温度、萃取时间、流体流量等工艺条件对萃取效率和产品质量的影响.得出最佳工艺条件,采用萃取压力25～30 MPa,萃取温度55～60℃,流体流量5 L/h,萃取5～6 h,萃取效率可以达到95％,可以得到质量分数大于95％的乙基香兰素产品.     

二氧化碳超临界萃取酸性水溶液中3-甲氧基-4-羟基苯甲醛的研究

采用二氧化碳超临界萃取酸性水溶液中3-甲氧基-4-羟基苯甲醛(香兰素),含有3-甲氧基-4-羟基苯甲醛的水溶液与超临界二氧化碳流体在萃取柱中连续逆流混合,研究得出最佳工艺条件:压力(22～26)MPa;萃取温度55～60℃,超临界流体与原料液体质量比5.5:1,此条件下,萃取效率95%以上,可以得到质量分教大于90%的产品.     

超临界CO2萃取丁香挥发油的实验研究

采用正交实验法对超临界CO2萃取丁香挥发油的条件进行了研究。考察了萃取温度、压力、CO2流量等因素在不同水平下对丁香挥发油提取率的影响。得到了超临界C02萃取丁香挥发油的最佳实验条件：萃取压力30MPa、温度40℃、CO2流量40kg／h和萃取时间80min,得率为20．62％。与水蒸气蒸馏法比较,超临界CO2萃取的收率高,萃取时间短。     

Drying processes for preparation of titania aerogel using supercritical carbon dioxide

Supercritical carbon dioxide drying was performed for the preparation of titania aerogels from sol–gel routes. The conditions of supercritical carbon dioxide drying were 313–323 K and 7.8–15.5 MPa. The solvents in titania wet gels obtained from the sol–gel routes were replaced by acetone. The titania aerogels obtained from supercritical carbon dioxide drying form needle-like structures. In supercritical carbon dioxide drying, the extraction rates of acetone from the wet gels were measured by using an on-line Fourier transform infrared spectroscope. It was found that the titania aerogels with lower cohesion were induced from the formations of homogenous phase for carbon dioxide + acetone system and the lower extraction rates of acetone. Furthermore, titania films were prepared by the depositions of the titania aerogels on ITO-coated PET substrates. The needle-like aerogels with lower cohesion derive the titania film with high surface area.     

Purification of hydrocarbons from aromatic sulfur compounds by supercritical carbon dioxide extraction

Supercritical carbon dioxide extraction to purify samples of model hydrocarbons (tetralin, decalin, and tetradecane) containing various aromatic sulfur compounds (benzothiophene, dibenzothiophene, and 4,6-dimethydibenzothiophene) was studied. The influence of extraction temperature and pressure was investigated for the extraction from a tetralin-dibenzothiophene system in the range of 293-353 K and 8-15 MPa, and it was found that the amount of tetralin extracted increased with an increase in carbon dioxide density, while the separation factor decreased with an increase in carbon dioxide density. High recovery and high separation factor values for the tetralin-dibenzothiophene system were obtained under 10 MPa at 313 K. Higher separation factor was obtained for tetralin than decalin and tetradecane, containing 4,6-dimethyldibenzothiophene than that containing dibenzothiophene.     

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.     

Lipase-catalysed hydrolysis of blackcurrant oil in supercritical carbon dioxide

The effect of reaction conditions on the extent of conversion in hydrolysis of blackcurrant oil was investigated. The enzyme used was Lipozyme, a lipase from Mucor miehei immobilised on macroporous anionic resin. The reaction was carried out in a continuous flow reactor at 10- and 30-50°C with carbon dioxide saturated with oil and water (55-100%) flowing up through the enzyme bed. Analysis of product composition indicated unfavourable hydrodynamics with significant mixing in the reactor when solvent interstitial velocity was lower than , while above this velocity value the flow pattern was near to plug flow. Lipase stability was very good with no activity reduction observed during a long-term experiment. The reaction rate was a function of the ratio of enzyme load to solvent volumetric flow rate. A complete hydrolysis of oil was achieved in the experiments carried out with the enzyme load of and CO₂ flow rate of 0.4-. The effects of pressure (10-) and temperature (30-40°C) on the reaction rate were small, and the effects of CO₂ saturation with water and of enzyme distribution in the reactor were negligible. Lipozyme displayed specificity towards linolenic acids; the release of α-linolenic acid was faster and that of γ-linolenic acid slower than the release of other constituent acids present in blackcurrant oil.     

Mass transfer and hydrodynamic study of supercritical carbon dioxide extraction of 1,8-cineole from small cardamom seeds

This study investigates mass transfer and hydrodynamic parameters of supercritical carbon dioxide (sc-CO₂) extraction of 1,8-cineole from small cardamom seeds (SCs). Solubility of 1,8-cineole in sc-CO₂, its diffusivity, and release kinetics from SCs have been explored. A correlated Chrastil equation has been developed for predicting solubility under varying extraction conditions. Empirical correlations among Reynolds, Schmidt, and Sherwood numbers considering Wilke–Chang equation for diffusivity showed a better fit as compared with those obtained using Stokes–Einstein equation. The extraction kinetics was in agreement with the Sovová model showing plug flow behavior. Release kinetics of 1,8-cineole from SCs was best explained by the Higuchi model. A high R² value (0.93) of the empirical equation involving dimensionless numbers suggested that the extraction process has been satisfactorily modeled. This model would help in scaling up the production of this significant biotherapeutic molecule from cardamom and similar seed matrices.     

Furfural production by acid hydrolysis and supercritical carbon dioxide extraction from rice husk

The aim of this research was to study the effect of furfural production from rice husk by hydrolysis accompanying supercritical CO₂ (SC-CO₂) extraction. The two-level fractional factorial design method was used to investigate the production process carried out with respect to furfural yield. The process variables are temperature range of 373–453 K, pressure 9.1–18.2 MPa, CO₂ flow rate 8.3 × 10⁻⁵–1.7 × 10⁻⁴ kg/s (5–10 g/min), sulfuric acid concentration 1 to 7 (%wt) and ratio of liquid to solid (L/S) 5 : 1 to 15 : 1 (vol/wt). The results obtained from the experimental design showed that increasing temperature, pressure, CO₂ flow rate and sulfuric acid concentration but decreasing ratio of liquid to solid would improve furfural yield. Moreover, furfural production by two-stage process (pre-hydrolysis and dehydration) can improve furfural yield further to be around 90% of theoretical maximum.     

超临界CO_2流体萃取沙棘油实验研究

建立了一套超临界流体萃取实验装置。就沙棘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、装填量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 ,并就工艺参数对萃取率的影响机理和原因进行了分析与讨论     

Continuous extraction of glycerol acetates from their mixture using supercritical carbon dioxide

Supercritical carbon dioxide was used for partially selective extraction of triacetin from a mixture of triacetin, diacetin, and monoacetin with a molar ratio of 1:2:1. The extraction was carried out in two stages. In the first stage, a central composite design was used to optimize the four variables of pressure, temperature, liquid CO₂ flow rate, and extraction time at three levels using a semi-continuous, supercritical carbon dioxide extraction setup. The composition of the extract under the predicted optimum conditions (i.e., 109 bar, 56 °C, 0.86 mL min⁻¹, and 61 min) was about 69% triacetin accompanied by only 30% diacetin and no detectable monoacetin. In the second stage, the effect of the two factors, pressure (100, 109, and 140 bar) and liquid CO₂ flow rates of 0.86 and 1.5 mL min⁻¹ measured at average laboratory temperature (27 °C) and pressure (0.89 bar), were studied using a continuous, supercritical carbon dioxide fractionation setup equipped with a glass-bead packed column kept under a thermal gradient of 56-70 °C. The experimental design was organized as a 3 × 2 general factorial design. Under the best conditions (i.e., 140 bar and 1.5 mL min⁻¹), the extraction yield of triacetin and diacetin were 41.8 and 3.0%, respectively, without any detectable monoacetin as verified by GC-FID.     

Influence of pretreatments for extraction of lipids from yeast by using supercritical carbon dioxide and ethanol as cosolvent

Saccharomyces cerevisiae is one of the most studied and industrially exploited yeast. It is a non-oleaginous yeast whose lipids are mainly phospholipids. In this work, the extraction of yeast lipids by supercritical carbon dioxide (SCCO₂) and ethanol as a co-solvent was studied. In particular our attention was focused on the selectivity toward triglycerides, and in a subsequent extraction of the phospholipids present in the yeast. Indeed CO₂ is a non-polar solvent and is not an efficient solvent for the extraction of phospholipids. However, SCCO₂ can be used to extract neutral lipids, as triglycerides, and the addition of polar co-solvents like ethanol, at different compositions, allows a more efficient extraction of triglycerides, and also an extraction-fractionation of phospholipids. In this work SCCO₂ extractions of a specific membrane complex of S. cerevisiae, obtained from an industrial provider, were carried out at 20 MPa and 40 °C, using ethanol as a co-solvent (9%, w/w). It was shown that different pretreatments are necessary to obtain good extraction yields and have a great impact on the extraction. The kinetic of the extractions were successfully modeled using Sovova's model. From the fitting of the main parameters of the model it was possible to compare the effects of the pretreatments over the yeast material, and to better understand the extraction process. Among the seven tested pretreatments the more appropriate was found to be an acid hydrolysis followed by a methanol maceration.     

Synthesis of biodiesel in supercritical alcohols and supercritical carbon dioxide

Biodiesel was synthesized in supercritical fluids by two routes: non-catalytically in supercritical alcohols and by enzyme catalysis in supercritical carbon dioxide. Two oils, sesame oil and mustard oil, and two alcohols, methanol and ethanol, were used for the synthesis. Complete conversion was observed for synthesis in supercritical alcohols whereas only a maximum of 70% conversion was observed for the enzymatic synthesis in supercritical carbon dioxide. For the synthesis in supercritical alcohols, the activation energies and pseudo-first order rate constants were determined. For the reactions in supercritical carbon dioxide, a mechanism based on ping pong bi-bi was proposed and the kinetic parameters were determined.     

Simulation of a supercritical carbon dioxide extraction plant with three extraction vessels

Although SuperCritical (SC) Fluid Extraction (SCFE) has been successfully applied commercially the last three decades, there is no systematic procedure or computational tool in the literature to scale-up and optimize it. This work proposes an algorithm to simulate dynamics in a multi-vessel (≥3) high-pressure SCFE plant where extraction vessels operate in batches, and is thus forced to use simulated-countercurrent flow configuration to improve efficiency. The algorithm is applied to a three-vessel SCFE plant using a shrinking-core model to describe inner mass transfer in the substrate. As example, the extraction of oil from pre-pressed seeds using SC CO₂ at 313 K and 30 MPa is simulated. After three cycles the process reaches a pseudo-steady-state condition that simplifies the estimation of plant productivity. Use of a three- instead of two-vessel SCFE plant increases oil concentration in the stream exiting the plant and decreases CO₂ usage at the expense of increasing extraction time.     

Supercritical carbon dioxide essential oil extraction of Lamiaceae family species: Mathematical modelling on the micro-scale and process optimization

In this paper the essential oil supercritical carbon dioxide extraction from leaves of Lamiaceae family species was studied. Recent investigations of Lamiaceae family essential oil storage have shown that most of the oil is found in peltate glandular trichomes on the leaf surface. The effect of supercritical CO₂ on the peltate glands was investigated by Scanning Electron Microscopy. It was observed that exposure to supercritical CO₂ led to disruption of the peltate glands and essential oil release. This phenomenon was used as a basic hypothesis of the mathematical model of the supercritical fluid extraction with CO₂. The model was applied to simulate basil, rosemary, marjoram and pennyroyal supercritical CO₂ extraction on the existing experimental data. An average deviation from the experimental data was less than 0.83%. The model results indicated a possibility of a decrease in the supercritical CO₂ consumption by modified and optimized processing of Lamiaceae family herbaceous material.