溶解度参数法计算超临界流体的溶解度

溶质在超临界流体中的溶解度计算方法有热力学模型和经验公式2种,其中经验公式法形式简单,精度接近甚至高于热力学模型,应用广泛。以往的经验公式多用超临界流体密度来关联溶解度,文中选择以溶解度参数为变量,用3个与温度无关的可调参数,建立了超临界流体溶解度计算的经验公式。计算的11种固体在超临界CO2、乙烷和乙烯中溶解度与实验数据的平均相对误差在10%左右。与密度相比,溶剂与溶质的溶解度参数差更能直观地反映出超临界流体对物质的溶解能力,且具有明确的理论基础,应该引起足够的重视和推广。     

乙醇-水溶剂中5'-尿苷酸二钠溶解度测定与关联

采用内置双光路激光检测器,在293.2-318.2 K温度范围内,测定了5'-尿苷酸二钠在纯水及不同乙醇-水混合溶剂中的溶解度.分别用R-K方程、λh方程和Wilson方程3种溶解度模型,采用最小二乘法关联实验数据,并对比不同溶解度模型.结果表明,在乙醇质量分数为0-0.65区间内,5'-尿苷酸二钠溶解度随着温度的升高而增大,随乙醇质量分数的增大而显著减小,λh方程对5'-尿苷酸二钠溶解度关联效果最好.将λ,h表达为乙醇质量分数的函数,并用于内插计算,精度满足工程要求.     

Solubility of supercritical gases in polymers—a review

Processing of polymers is greatly affected by the presence of dissolved gases. Analysis of the effect of dissolved gases requires two types of information: equilibrium thermodynamic data and predictive correlations as well as diffusion rate data and analyses. We review here the state-of-the-art knowledge of the equilibrium thermodynamics of gases dissolved in polymers. The published data are presented and analyzed. Also, we review the latcst theories and predictive correlations for gas solubility in polymers.     

Solubility of astaxanthin in supercritical carbon dioxide

The solubility of astaxanthin in carbon dioxide was measured under supercritical conditions of a pressure range from 80 to 300 bar, and temperature range from 303 to 333 K, by using a dynamic flow-type. The solubility of astaxanthin increasing from 0.42×10⁻⁵ to 4.89×10⁻⁵ with higher temperature and pressure maintains certain density of supercritical carbon dioxide. The solubility data obtained were applied to the Chrastil model, based on the density of carbon dioxide. The data fitted well with the Chrastil model at most experimental conditions.     

Solubility of supercritical gases in organic liquids

Chrastil (1982) [6] demonstrated that the solubility of a substance in a supercritical fluid (SCF) can be correlated with the density of the pure supercritical gas. Therefore, Chrastil's equation permits calculation of the supercritical phase composition of binary SCF + substance mixture based on the knowledge of the supercritical gas density and avoiding the use of equation of state based models.In this work, it is demonstrated that the supercritical fluid density also defines the liquid phase composition of binary systems; a density-dependent relationship is presented to calculate the solubility of supercritical gases in organic liquids. The isothermal solubility of several gases commonly employed in supercritical processing, such as carbon dioxide, methane, and ethane, in different organic liquids, including alkanes, alkenes, alcohols, acids, ketones, esters, terpenes and aromatic compounds, was successfully correlated as a function solely of the pure supercritical fluid density. As an application, pressure vs. composition phase diagrams of binary SCF + substance mixtures were obtained circumventing the use of equation of state models.     

水在超临界二氧化碳中的溶解度

生物柴油副品油酸的高值化利用是降低生物柴油成本的有效途径之一,为了充分利用生物柴油副品油酸中的壬二酸,用基于超临界流体技术(SCCO2)的固相缩聚方法可制得超高相对分子质量的尼龙69等高分子材料。SCCO2不仅可以作为增强SSP过程的介质使用,还可以有效地将缩聚物(如水等小分子缩聚物)脱除,促进反应的进行,因此测定水在超临界二氧化碳中的溶解度对研究SCCO2增强的SSP过程具有重要意义。文中采用静态法测定了水在超临界二氧化碳中的溶解度,温度为313.15,333.15,353.15,373.15 K,压力为8.0—18.0 MPa,溶解度(摩尔分数)为0.254%—1.414%;探究了温度、压力对溶解度的影响,结果表明:溶解度随温度、压力的升高而升高;利用PR状态方程和Chrastil修正模型对溶解度进行了计算,结果表明溶解度的计算值和实验值吻合良好,平均相对误差分别为4.63%和5.89%。     

Homogeneously-catalyzed syntheses in supercritical fluids

Supercritical fluids (SCFs) differ from liquid solvents in a number of important properties, any of which could potentially alter the performance of a chemical reaction performed in a supercritical medium. Although rate, yield and selectivity improvements as well as environmental, health and engineering benefits are all possible, little research has been reported on homogeneously-catalyzed syntheses in SCFs. Several notable successes plus new techniques for solubilizing hydrophilic reagents in SCFs are encouraging further research in this growing field. This revised version was published online in June 2006 with corrections to the Cover Date.     

超临界流体中的化学反应

超临界流体中的化学反应可分为两大类 ,即超临界流体作为反应介质的反应和超临界流体作为反应原料的反应 ,分别介绍了其研究进展 ,着重介绍了第一类反应中的酶催化反应、超临界水氧化、高分子合成     

One-fluid mixing rules for cubic equations of state: II. Solubility of solid mixtures in supercritical fluids

Three cubic equations of state are carefully examined to evaluate their capability for correlating the solubility of solid mixtures in supercritical fluids. After obtaining the pure solute-solvent interaction parameters, the solute-solute interaction parameters were directly calculated from the experimental ternary solubility data. The Redlich-Kwong, Soave, and Peng-Robinson equations of state correlate well the ternary data. However, the Redlich-Kwong equation of state gives the best result among them.     

One-fluid mixing rules for cubic equations of state: I. Solubility of pure solids in supercritical fluids

Three cubic equations of state are carefully examined to evaluate their capability for correlating the supercritical solubility data of solid solutes in compressed gases. The overall average absolute deviatons between experimental and predicted values for 35 binary systems are 17.33% (Redlich-Kwong), 22.92% (Soave), and 22.93% (Peng-Robinson) using one binary parameter and 12.55% (Redlich-Kwong), 15.57% (Soave), and 13.71% (Peng-Robinson) using two binary parameters.     

Solubilities of solids in supercritical fluids

The solubilities of several low-volatility compounds in supercritical fluids were measured. The fluids used were pure carbon dioxide or carbon dioxide modified with small amounts of organic liquids. Some enthalpies of solution of solids in carbon dioxide at a density of 0.80 g/mL are presented. The enthalpy of solution of fluoranthene in carbon dioxide was found to be less endothermic at higher CO₂ density. The order of solubilities in the modified fluids was the same as that in the pure liquid modifiers. The same apparatus was used to measure vapor pressures of some substances as well as solubilities.     

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.     

Solubility of simple and mixed triacylglycerols in supercritical CO2

A simple mixture of triacylglycerols (TAGs) was synthesized enzymatically from palmitic acid and oleic acid. The mixture contained tripalmitoylglycerol (PPP), trioleoylglycerol (OOO), and various isomers of palmitoyl-dioleoylglycerol (POO) and oleoyl-dipalmitoylglycerol (PPO). The behavior of this TAG mixture in equilibrium with supercritical carbon dioxide (SF-CO₂) was studied at 40 and 60°C between 172 and 310 bar. Generally, the partition coefficients varied inversely with species molecular weight. The solubilities of PPP and OOO in SF-CO₂ were determined at the same conditions. PPP was markedly more soluble in SF-CO₂ when present in the TAG mixture than as a pure compound.     

超临界流体在超细粉体制备中的应用

对超临界流体用于制备超细粉体的研究现状和主要研究成果进行了综述。介绍了近年来开发的一些新方法和新工艺 ,其中包括超临界溶液快速膨胀 (RESS)法 ,超临界流体脱溶 (SAS)法 ,超临界逆向结晶 (SRC)法 ,超临界干燥 (SD)法和超临界流体化学反应等。分析了这些新工艺新方法的原理、特点 ,技术上的可行性 ,应用前景 ,目前达到的水平与存在的问题 ,及今后发展需解决的关键问题等。     

超临界流体在制膜过程中的应用

介绍了超临界流体诱导相分离过程制备有机膜的工艺流程、原理及特点,并与传统的沉浸凝胶相转化制膜方法进行了比较。同时介绍了超临界流体过程在有机膜的制备和改性方面的研究现状及其研究前景,并对其进一步的研究提出了一些建议。     

Liquefied gases and supercritical fluids in oilseed extraction

Soybean oil and numerous other vegetable oils can be extracted from crushed seeds by means of liquefied gases or supercritical fluids. The oils are recovered by lowering the pressure or increasing the temperature, or both. Supercritical carbon dioxide is ideally suited for the food industry as it is nontoxic and nonflammable. Moreover, it can be removed easily from the oil as well as the meal. The oils extracted with supercritical carbon dioxide contain much lower proportions of phospholipids than those obtained by conventional processing with hexane. The addition of acetone or another carrier or entrainer aids in the fractional extraction of lipids differing in polarity. The range of applicability of liquefied gases and supercritical fluids in the extraction and fractionation of lipids should be explored further to develop industrial processes using these solvents.     

Particle size design of digitoxin in supercritical fluids

Bioavailability of the pharmaceutical substances is very important for their activity. In case of necessity, bioavailability can be improved by reducing the particle size of the drugs. In this study, particle size of digitoxin was reduced by the Rapid Expansion of Supercritical Solutions (RESS). The effects of pre-expansion temperature (90-110 °C), flow rate (2.5-7.5 ml/min), spray distance (3-7 cm) on the size and size distribution of the precipitated digitoxin particles were carried out. The particles were characterized by dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and LC-MS analysis.While the particle size range of the original digitoxin was 0.2-8 μm, it was decreased to 68-458 nm and determined that 97% of the particles were below 200 nm depending on the different experimental conditions.Response surface method (RSM) was used to optimize the process parameters. The flow rate, 7 ml/min; spray distance, 7 cm; pre-expansion temperature, 95 °C were found to be the optimum conditions to achieve the minimum particle size of digitoxin.     

Enantioselective hydrogenation of ethyl pyruvate in supercritical fluids

The enantioselective hydrogenation of ethyl pyruvate to (R)-ethyl lactate has been studied using gases under supercritical conditions as solvents. The catalyst was a 5 wt% Pt/alumina modified with cinchonidine. In supercritical ethane the reaction time could be reduced by a factor of 3.5 compared to toluene under similar conditions, without any loss in enantioselectivity. A further advantage of ethane is that the enantioselectivity remains high even at high catalyst/reactant ratio, which is interesting in view of a possible application of a continuous fixed-bed reactor for this reaction. A strong catalyst deactivation was observed in supercritical CO₂, which is due to the reduction of CO₂ on Pt as indicated by FTIR.     

溢流法测定超临界CO_2在聚己酸内酯中的溶解

以超临界CO2作为溶剂,采用溢流法研究聚己酸内酯(PCL)在CO2中的溶胀过程和超临界CO2/PCL体系的热力学平衡规律。考察了温度、压力对溶解度的变化趋势,分析加入有机溶剂后对CO2在聚合物中的溶解度的影响,并应用P-T(Patel-Teja)方程作为热力学模型分析和计算溶解规律。结果表明:CO2的溶解度随温度升高而降低,随压力增大而增大,有机溶剂的加入能够进一步提高CO2的溶解度,在相同的温度压力条件下,加入相当于CO2质量的2.26%的二氯甲烷,最多可使溶解度增加28.06%。在温度313.15—353.15 K、压力10—20 MPa范围内,P-T方程能较好地预测CO2在PCL中的溶解度,其相对误差在-12.53%—12.01%。     

Characterization of copolymers fractionated using supercritical fluids

In this study supercritical fluids were used to process several different types of oligomers. Supercritical fluid processing was found to be quite effective at removing low vapor pressure monomers from polymers and for fractionation of polymers according to molecular weight. This resulted in high purity materials with low M?_w/M?_n ratios. The polymer fractions obtained were analyzed by size exclusion chromatography, differential scanning calorimetry, and melt rheometry. Their physical and chemical properties are described.