超临界流体中物质溶解度的研究(Ⅰ)

本文分析了超临界流体萃取过程的特点.认为超临界流体的P-V-T行为可采用某种气体状态方程来描述.在分离作用机理上更近于液液萃取过程.提出了其萃取历程的物理化学模式,据此推导了超临界流体中物质溶解度计算公式.通过对此式的剖析和简化,得到了固体及液体纯物质在超临界流体中溶解度的半理论、半经验计算公式.并用文献发表的实验数据对半经验式的适用性进行验算,获得了较满意的结果,平均偏差≤10%.     

Generalizing Binary Solubility Data for Low-Volatile Liquids in Supercritical Fluids

Experimental data on the binary solubilities of a large number of low-volatile liquids in supercritical solvents (carbon dioxide and propane) are generalized by the entropy method of the similarity theory over wide temperature and pressure ranges. Two groups of similar systems are revealed which correspond to different entropy ranges of the pure solvent. The mechanism of the dissolution of liquids in supercritical fluids was found to be mainly physical.     

Density-Based Correlation for Solid Solubility in Supercritical Solvents

Abstract

The use of solvents at conditions above their critical points is increasing because of their increased dissolving power and enhanced transport properties, as in caffeine extraction, etc. This research sought an improved method for correlating the solubility of materials in light solvents from conditions below the critical point of the solvents to those above it, especially to facilitate prediction, interpolation, and extrapolation of solubility data better than existing equations. Solvent density was recognized early as a factor in solvent dissolving power but not used as a correlating parameter. A density approach based on mass-action equilibrium law employing the solvation concept was used to correlate the data on selected binary mixtures with excellent results. For high pressures the relationship yields a plot of log solute solubility (g/L solution) versus log solvent density (g/L solution) which is sectionwise linear. A simplification of the relationship applies well at lower pressures. For both regions, experimental data are represented more easily and better than by conventional equations of state.     

超临界流体色谱法测定固体在二氧化碳中的溶解度

开发了一种测定超临界二氧化碳中大分子溶质的溶解度的方法。这一方法将微型超微界流体萃取直接与超临界色谱相耦合，超临界流体色谱采用ＦＩＤ作为检测器。实验中两者具有同一压力、温度及同样的ＣＯ２流速度。     

固体在超临界二氧化碳中溶解度的关联与计算

精确的溶解度数据是超临界流体萃取工艺设备设计和操作条件选择的关键 ,本文采用Peng -Robinson状态方程对 15种固体在超临界CO2 中的溶解度数据进行了关联计算 ,溶解度的计算值与文献的实验值符合很好 ,其平均相对偏差均小于 10 %。     

Measurement and Correlation of Solid Drugs Solubility in Supercritical Systems

A dynamic experimental set-up was utilized to measure ibuprofen solubility in supercritical CO2 at the pressure range of 8-13 MPa and the temperatures of 308, 313 and 318 K. Mole fraction values varied from 0.015＆#215;10^-3 to 3.261＆#215;10^-3 and correlated by using seven different semi empirical equations of state （Bartle, Modi-fied Bartle, Mendez-Teja, Modified Mendez-Teja, Kumar-Johnson, Sung-shim and Gordillo） as well as seven cubic equations of state （van der Waals, Redlich-Kwong, Soave-Redlich-Kwong, Peng-Robinson, Stryjek-Vera, Patel-Teja-Valderana and Pazuki）. Single and twin-parametric van der Walls mixing rules （vdW1, vdW2） were ap-plied in order to estimate the supercritical solution properties. The physicochemical properties were also obtained using Joback, Lydersen and Ambrose methods. Absolute average relatives deviation （AARD） were calculated and compared for all the correlating systems. Results showed that among the cubic equations of state （EOSs） the Pazuki equation （AARD=19.85% using vdW1 and AARD=8.79% using vdW2） and SRK equation （AARD=19.20%using vdW1 and AARD=10.03%using vdW2） predicted the ibuprofen solubility in supercritical CO2 with the least error in comparison to the others. Among the semi-empirical EOSs the most desirable deviation （AARD〈10%） was obtained by using Modified Bartle and Modified Mendez-Teja equations in all the studied temperatures.     

Removal of Pollutants from Solid Matrices Using Supercritical Fluids

Abstract

Several supercritical fluid extraction (SCFE) processes have been proposed for removing toxic and intractable organic compounds from a range of contaminated solids. These include soil remediation and the regeneration of adsorbents used to treat wastewater streams such as granular activated carbon (GAC). As a separation technique for environmental control, SCFE has several distinct advantages over conventional liquid extraction methods and incineration. Most notably, the contaminant is removed from the solvent in a concentrated form via a change in pressure or temperature and can be completely separated upon expansion to atmospheric pressure.

The viability of SCFE hinges on process conditions such as solvent-feed ratio and solvent recycle ratio. The necessity of recycling solvent complicates the contaminant separation step since a complete reduction to atmospheric pressure would create large recompression costs. Because of this, the pressure and temperature dependence of contaminant solubility must be understood so that operating conditions for the separation step can be defined. Fortunately, this is the most developed aspect of SCF technology. However. the mass transfer limitations to removing contaminants from solids change with solvent flow rate.

This paper discusses the use of SCFE for environmental control and presents results for the removal of DDT and 2-chlorophenol from GAC. 2-chlorophenol is almost completely removed with pure CO₂ at 40°C and 101 bar while only 55% of the DDT is removed at 40°C and 200 bar. These differences in regeneration efficiency cannot be understood solely in terms of solubility but point to a need for detailed studies of adsorption equilibrium and mass transfer resistances in supercritical fluid systems.     

夹带剂对超临界流体中固体溶解度的作用分析

测定了2-羟基苯甲酸在308.15K和328.15K,10.0-25.0MPa条件下,在含和不含夹带剂的超临界CO2中的溶解度数据;分析了夹带剂对超临界流体中固体溶质溶解度的作用机理,得到选择夹带剂的一般原则。     

固体溶质在超临界流体中溶解度计算方程的改进

关于固体物质在超临界流体 ( SF)中溶解度计算方程的改进 ,是在以相平衡为基础的两参数模型方程基础上提出了一个四参数的改进式 ,其中 ,两个普遍化参数用于修正模型简化及估算误差产生的偏差 ;用P- R方程计算逸度系数时将相互作用能参数 Kij修正为 sin ( Kij) ,可使计算搜索快捷准确。利用文献中 2 0组二元物系试验数据对改进模型进行了验算 ,结果表明关联精度明显优于原来的方程     

流动法测定固体在超临界二氧化碳中的溶解度

建立了一套流动法测定固体物质在超临界CO2 中溶解度的实验装置。该装置用高压六通阀取样 ,特别适用于测量溶解度较小的固体物质。以萘为溶质 ,在 32 8K时对装置进行了验证 ,实验结果与文献值基本相符。装置的工作温度 0～ 80℃ ,工作压力 0 .1～ 40MPa。     

MCI法计算固体溶质在超临界CO2中溶解度的研究

修正了杂原子原子点价（Ai^E）的计算方法，提出了一个新的分子连接性指数（^kχ^E）。该指数物理意义明确，易于计算，具有良好的结构选择性。用MCI法研究了固体溶质在超临界CO2中的溶解度与其结构之间的关系，研究结果表明溶质的分子连接性指数（^4χPC^E）可用来关联溶质苯环上取代基的种类、位置、长度对溶解度的影响，计算结果表明修正杂原子点价计算方法后的模拟结果比用原来的原子点价计算得到的偏差降低了5．01％。     

应用BP神经网络预测固体在超临界流体中的溶解度

构造Vogl快速算法误差反向传播(EBP)神经网络,应用该神经网络对若干固体在超临界流体中的溶解度进行预测,对21体系共612个数据点进行训练和预测,预测的总平均相对误差为4.02％,优于状态方程法所计算的结果。     

Modeling of the Oxidation of Organic Compounds in Supercritical Water

A system for oxidation of organic impurities in supercritical water is proposed. Models are formulated and calculations are performed to determine the characteristics of the main apparatuses of the system, namely, heat exchangers, a chemical reactor, and a separator. The models take into account specific features of processes under supercritical conditions, specifically, the changes in the thermodynamic properties (enthalpy, specific heat, critical parameters) of the reaction mixtures with changes in pressure and temperature, and also the variations of the compositions of the mixtures along the lengths of the apparatuses. The thermodynamic properties are calculated by methods of nonequilibrium thermodynamics. A numerical analysis is performed of one of the variants of a system for acetic acid oxidation by oxygen in supercritical water, which can be a prototype of a pilot plant. The fuel is chosen to be an aqueous methanol solution, and the oxidant is taken to be hydrogen peroxide. Replacement of the reactant, the fuel, or the oxidant does not fundamentally change the methods for calculating the characteristics of the apparatuses and the entire system.     

超临界流体技术在分离工程领域中的应用

文章阐述了超临界流体分离技术的原理、流程与特点.综述了该技术在分离工程领域的应用方向、存在的问题及未来的发展前景.指出了该技术兼具精馏和萃取两种分离作用效果,在天然资源成份的分离提取、脱除有害成份或杂质、清洗、色谱分析等诸多领域部有着其独特的开发应用优势.     

超临界流体在聚合物残单和挥发物脱除过程中的应用

综述了超临界流体在聚合物加工中的优势及其脱除聚合物残单和挥发物的原理和步骤,着重介绍了其在脱除聚合物残单和挥发物中的应用、脱除效果和发展趋势,提出了优化过程的方法,并评估其应用的经济性。