苯乙烯在超临界CO2中的溶解度

测定了温度为 32 3.15、 32 8.15、 333.15K ,压力为 3.0～ 2 4 .0MPa条件下苯乙烯 (ST)在超临界二氧化碳 (SC -CO₂ )中的溶解度 ,并根据溶剂化缔合概念、相平衡规则及高压对缔合平衡移动的影响导出溶解度数学模型 .本模型的ST溶解度预测值与实验值吻合良好 .用文献发表的溶解度数据对模型的适用性进行验算 ,也获得了较为满意的结果     

阿魏酸和川芎嗪在超临界CO2中溶解度的测定

采用动态法分别测定了阿魏酸和川芎嗪在超临界CO2中的溶解度.实验结果表明在压力10～35MPa和温度308.15～338.15K范围内,阿魏酸在超临界CO2中的溶解度(摩尔分数)为6.936×10(7～26.527×10(7;在压力10～30MPa和温度318.15～338.15K范围内,川芎嗪在超临界CO2中的溶解度(摩尔分数)为0.010～0.131.阿魏酸在超临界CO2中的溶解度随着压力的增加而增大;温度对阿魏酸溶解度的影响较为复杂,出现了交迭压力行为.而川芎嗪在超临界CO2中的溶解度在实验范围内没有出现交迭压力行为.采用Chrastil方程分别对阿魏酸和川芎嗪在超临界CO2中的溶解度数据进行了关联,其AARD值分别为12.92%和4.23%.     

超临界CO2在聚合物中的溶解度和扩散性研究

用重量分析法测量了静态条件下CO2在聚苯乙烯(PS)中的溶解度,研究了溶解度与压力和温度的关系,估算了CO2在聚合物PS中的扩散系数。用Henry系数表示了溶解度与温度的关系。实验压力在5-30MPa范围、温度在40-200℃范围。实验数据表明:CO2在PS中的溶解度随着压力的增加而增加,但随着温度的增加而降低。CO2在PS中的扩散系数随饱和时间增加而增加。当吸附量达到一定值时,扩散系数呈下降趋势。     

超临界CO2萃取丁香油的数值模拟

为了预测超临界CO₂萃取挥发油动态过程,根据挥发油在超临界CO₂与物料之间的质量传递平衡,采用集总参数法建立超临界CO₂萃取丁香油过程的数学模型。结合不同温度、压力、粒径和CO₂流速条件下的实验结果,对方程进行了合理的简化,并利用实验数据拟合出模型中CO₂密度、粒径和流速的系数。验证结果表明模型的计算值和实验值的平均相对误差在6. 88%～57. 78%之间,建立的数值模型能较好地描述实际的超临界CO₂萃取丁香油行为。     

胆甾醇在超临界CO2中的溶解度测定与关联

利用动态法测定了胆甾醇在超临界CO2中的溶解度。在10—30 MPa,313—343 K下,胆甾醇的溶解度摩尔分率为10-6—10-4。引入与密度有关的混合规则,将二元交互参数表示为密度的函数,采用PR状态方程,关联胆甾醇在超临界CO2中的溶解度。改进后的溶解度模型克服了采用经典混合规则的PR方程不能很好地关联胆甾醇大分子物质的缺陷,大大提高了关联精度。     

α—细辛醚在超临界CO2中溶解度测定

测定了α－细辛醚在超临界CO2中的溶解度。考察了压力,温度等因素对α－细辛醚在超临界CO2中溶解度的影响。结果表明α－细辛醚在超临界CO2中的溶解度随着压力的增加而增大,随着温度的增加而减小,并符合经典的Chrastil表达式。     

齐墩果酸在超临界CO2中的溶解度研究

采用静态平衡差重法测定了齐墩果酸在超临界CO2中各个状态点的溶解度,考查了温度、压力、密度等因素对齐墩果酸在超临界CO2中溶解度的影响,并采用Chrastil模型对实验数据进行分析计算。实验结果表明：齐墩果酸在超临界CO2中的溶解度随着压力的增加而增加,20MPa条件下的密度与溶解度符合一定的函数关系。     

二乙基二硫代氨基甲酸钠在超临界CO2中的溶解度

利用动态法测定了超临界络合萃取中一种常用的络合剂?固体二乙基二硫代氨基甲酸钠(NaDDC.3H2O)在超临界CO2中的溶解度. 实验在308.15~328.15 K,10~30 MPa的范围内进行, 溶解度随温度、压力的增大而增大. 将实验结果用Chrastil缔合模型法进行关联,取得了比较好的关联精度.     

丁香油的超临界CO2萃取及其微胶囊的制备

在70℃和10 MPa条件下通过对丁香花蕾进行超临界CO2萃取得到丁香油,萃取率达19%～21%.气质联用分析结果表明,丁香油中主要化学成分包括丁香酚、β-石竹烯和乙酰基丁香酚等.以丁香油为囊芯,探讨利用干酵母细胞作为囊壁材料制备微胶囊的可行性.通过正交试验考察了包埋温度、包埋时间、丁香油与干酵母配比(芯材比)对微胶囊化丁香油的影响.结果表明,在包埋温度70℃、包埋时间9 h和芯材比为1∶1(w/w)的条件下,微胶囊中丁香油包埋率达到41.26%.通过扫描电镜观察,丁香油微胶囊呈规则的球形,大小均一,颗粒直径在2.0～4.0 μm.在100℃下对经微胶囊化的丁香油加热20 h,其挥发率只有15.04%,远低于相同条件下丁香油的挥发率(58.29%).这种新型的微胶囊化方法,具有制备过程简单、包埋率高和不引入有机溶剂的优点.     

阿昔洛韦在超临界CO2中的溶解度与关联

药物微粒化可改善其溶出度,提高生物利用度。为应用超临界流体技术制备阿昔洛韦(Acyclovir)微粒,用静态法测定了在313．15～413．15K,10．0～30．0MPa下阿昔洛韦在超临界CO2中的溶解度。阿昔洛韦的溶解度较小,在10^-5～10^-7(摩尔分率)之间,溶解度随着温度和压力的升高而增大,不存在文献报道的反向区。采用P-R方程对溶解度数据进行关联,平均相对误差为10．0％。     

Measurement and correlation of quaternary solubilities of dihydroxybenzene isomers in supercritical carbon dioxide

The equilibrium quaternary solubilities of dihydroxybenzene (resorcinol + pyrocatechol + hydroquinone + SCCO₂) isomers were experimentally determined at 308, 318 and 328 K over a pressure range of 9.8–15.7 MPa by using a saturation method. The effects of temperature, pressure and the components on each other have been thoroughly investigated. The selectivity of SCCO₂ for ternary (resorcinol + pyrocatechol + SCCO₂) and quaternary systems was discussed. A new model equation for quaternary solubilities of solids has been developed by accounting for non-idealities by combining the solution model with Wilson activity coefficient model. The model equation has five adjustable parameters and correlates the quaternary solubilities of current data along with two other quaternary data reported in the literature.     

Mathematical modeling and genetic algorithm optimization of clove oil extraction with supercritical carbon dioxide

In the present study, a mathematical modeling for extraction of oil from clove buds using supercritical carbon dioxide was performed. Mass transfer is based on local equilibrium between solvent and solid. The model was solved numerically, and model estimation was validated using experimental data. For optimization, the clove oil equilibrium constant between solid and supercritical phase was determined by a theoretical method using fugacity concept, consequently the genetic algorithm for obtaining optimal operational conditions was used. The optimal conditions which obtained the highest amount of clove oil were pressure of 10 MPa and temperature of 304.2 K.     

超临界环境下梯恩梯和黑索金的溶解度参数计算

动静态结合法测试了TNT、RDX在超临界CO2中的溶解度,测试温度分别为303.0,308.0,323.0,338.0 K,压力范围10.0~50.0 MPa,利用Bartle半经验模型对测量结果进行了关联,由Kumar and Johnston理论计算了2种物质在超临界CO2中的偏摩尔体积。结果表明,TNT和RDX溶解度的理论值和实验值具有良好的一致性,平均相对误差是3.72%和8.91%;在303.0,308.0,323.0,338.0 K温度下,TNT和RDX的偏摩尔体积分别为-6 942.61,-6 213.46,-5 438.49,-4 834.76 cm3/mol和-4 510.63,-3 894.52,-3 428.69,-2 631.85 cm3/mol。     

Measurements and correlation of effect of cosolvents on the solubilities of complex molecules in supercritical carbon dioxide

A new transparent microscale circulation-type high pressure equilibrium cell with on-line sampling was devised. With this apparatus, experimental solubility of molecularly complex species such as steroids (cholesterol, stigmasterol and ergosterol) and fatty acids (palmitic acid and stearic acid) in supercritical carbon dioxide(sc-C0₂) were measured. Also, to find an appropriate substance for enhancing both the polarity and the solubility power of the SC-CO₂ solvent, we arbitrarily selected three polar substances such as acetone, methanol and water and the effect of these cosolvents on the solubility of solutes in SC-CO₂ are examined. The supercritical phase equilibrium data of solute-cosolvent-sc-CO₂ systems were quantitatively correlated using a new equation of state based on the lattice fluid theory incorporated with the concept of multibody interaction. We found that the addition of tracer amount of acetone or methanol to SC-CO₂ enhances the solubility of all solutes about thirty to sixty times when compared with the case of pure sc-CO₂ However, for the case of cosolvent water, no further enhancement of the solubility of solutes was realized. Also, the versatile fittability of the equation of state proposed in this work was demonstrated with the newly measured ternary supercritical equilibrium data.     

Equilibrium distributions of key components of spearmint oil in sub/supercritical carbon dioxide

Effects of temperature (at 35, 45 or 55°C) and pressure (10–110 atm) on the relative distribution coefficients of the twelve key components of spearmint oil (essential oil ofMentha cardiaca; Scotch spearmint) at equilibrium in dense CO₂ were investigated under conditions ranging from subcritical to supercritical regions. Effects of vapor pressure, molecular weight and polarity of the key components on their equilibrium distributions in sub/supercritical CO₂ are discussed. At 35°C, all key components of spearmint oil are equally soluble in dense CO₂ within the 12–102 atm pressure region. At 45 and 55°C, the key components are equally soluble for pressures greater than about 60 atm. However, around either 45°C/27 atm or 55°C/35 atm conditions, the relative distribution coefficients of all monoterpene hydrocarbons and of isomenthone (an oxygenated monoterpene) exhibit maxima, which are due to significantly higher vapor pressures of these components and significantly lower solvating power of the dense-gas solvent at these particular temperatures and pressures. Vapor-pressure effects, coupled with the decrease in solvating power, dominate the effects of polarity and molecular mass of the key components. Deterpenation of spearmint oil with dense CO₂ is possible around either 45°C/27 atm or 55°C/35 atm, where the monoterpene hydrocarbons tend to concentrate in the CO₂-rich phase.     

超临界CO2萃取八角茴香油及其化学成分研究

用超临界CO2萃取(SFE-CO2)技术,在压力16 MPa、温度35℃、反应时间2 h及CO2流量30L/h的条件下,对八角茴香的果实进行了萃取,得到八角茴香萃取物,并用水蒸气蒸馏法提取八角茴香精油.对不同提取工艺得到的八角茴香产品的得率及质量进行了分析比较,结果显示SFE-CO2法产品得率高,为10.5%,而水蒸气蒸馏法仅为7.5%.用GC-MS分别对SFE-CO2萃取物和水蒸气蒸馏精油的化学成分及相对含量进行了测定,共鉴定出40种化合物超临界CO2萃取物有39个,其中大茴香脑质量分数为78.91%;水蒸气蒸馏精油有37个,大茴香脑质量分数为83.8%.     

Continuous supercritical carbon dioxide processing of palm oil

Crude palm oil was processed by continuous supercritical carbon dioxide. The process reduces the contents of free fatty acids, monoglycerides and diglycerides, certain triglycerides, and some carotenes. The refined palm oil from the process has less than 0.1% free fatty acids, higher carotene content, and low diglycerides. Solubility of palm oil in supercritical carbon dioxide increased with pressure. A co-solvent improves the refining process of palm oil.     

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.     

Characterization and supercritical carbon dioxide extraction of walnut oil

Walnut (Juglans regia L.) oil was extracted with compressed carbon dioxide (CO₂) in the temperature range of 308 to 321 K and in the pressure range of 18 to 23.4 MPa. The influence of particle size was also studied at a superficial velocity of 0.068 cm/s, within a tubular extractor of 0.2 L capacity (cross-sectional area of 16.4 cm²). FFA, sterol, TAG, and tocopherol compositions were not different from those of oil obtained with n-hexane. The main FA was linoleic acid (56.5%), followed by oleic acid (21.2%) and linolenic acid (13.2%). The main TAG was LLL (linoleic, linoleic, linoleic) (24.4%), followed by OLL (oleic, linoleic, linoleic) (19.6%) and LLLn (linoleic, linoleic, linolenic) (18.4%). The main component of sterols was β-sitosterol (85.16%), followed by campesterol (5.06%). The amount of cholesterol was low (0.31 and 0.16% for oils extracted by n-hexane and supercritical fluid extraction, respectively. The CO₂-extracted oil presented a larger amount of tocopherols (405.7 μg/g oil) when compared with 303.2 μg/g oil obtained with n-hexane. Oxidative stability determined by PV and the Rancimat method revealed that walnut oil was readily oxidized. Oil extracted by supercritical CO₂ was clearer than that extracted by n-hexane, showing some refining. A central composite, nonfactorial design was used to optimize the extraction conditions using the software Statistica, Version 5. The best results were found at 22 MPa, 308 K, and particle diameter (Dp) −0.1 mm.