氯的容积性质初探

叙述了气体、液体状态方程对液氯在不同温度条件的容积性质，并进行了研究，通过对其摩尔体积（密度）与文献值的对照，认为改良的范德华方程，改良的Ｒ－Ｋ方程及ＲＫＳ方程能较好地应用气相计算，Ｒａｃｋｅｔｔ方程及其修正式能比较好地应用于液相计算。     

二氧化碳与乙醇和异丙醇的二元汽液平衡

应用汽液双循环高压相平衡装置，测定了二氧化碳－乙醇和二氧化碳－异丙醇二元混合物分别在３０３．１５Ｋ，３１０．１５Ｋ和３２９．１５Ｋ，压力范围为１．７８～１０．０４ＭＰａ下的汽液相平衡数据。用ＤＤＬＣ－ＳＲＫ方程关联两个二元体系的汽液相平衡数据，计算值与实验值吻合良好。     

超临界二氧化碳萃取低挥发性液体混合物的相平衡

在半连续式实验设备中分别测定了苯甲醇－２－苯乙醇和苯甲酸酯－苯甲醇的等摩尔混合物与超临界ＣＯ２三元系相平衡数据。实验温度分别为３０８．２Ｋ和３１８．２Ｋ，压力范围为８～２０ＭＰａ。实验结果表明：对第一个三元系，两种液体在超临界ＣＯ２中的溶解度与ＣＯ２在液相中溶解行为密切相关；对第二个三元系，较高压力下，超临界流体相中苯甲酸甲酯浓度突然增大，而苯甲醇浓度变化不明显。通过引入考虑分子体积差别的二元作用参数，用Ｐｅｎｇ－Ｒｏｂｉｎｓｏｎ方程对气液平衡数据进行了关联。     

超临界流体特性及在有机溶剂中相行为研究

超临界流体具有许多独特的性质,如粘度、密度、扩散系数、溶剂化能力等性质随温度和压力变化十分敏感:粘度和扩散系数接近气体,而密度和溶剂化能力接近液体。本文通过实验首先进行了超临界二氧化碳与氟原子作用考察氟原子的引入对膨胀效果的影响、超临界二氧化碳与羰基作用,考察羰基对膨胀效果的影响、从而确定出最佳的共溶剂[1]。随后,使之与肉桂醛做一系列比例的膨胀对比实验。     

超临界流体改性高分子聚合物研究进展

超临界流体因兼具液体和气体特性而倍受关注。主要介绍二氧化碳、甲醇、水等超临界流体在高分子聚合物改性、废旧塑料/橡胶回收、纤维素水解及其他方面的应用,并展望了超临界流体在高分子材料领域的应用前景。     

细铁粉气液固三相磁场流化床的床层膨胀特性

研究了空气－水－细铁粉三相磁场流化床在两种气体分布器作用下的床展膨胀特性．结果表明,随着磁场强度的增强,细铁粉流化床层表现为散流区、链流区和磁聚区．气体在液体中的分散形态与气体分布器、气体速度和液体速度有关,表现为鼓泡、鼓泡－节涌和节涌．实验得到了链流区内气体在上述分散形态下的床层膨胀比（）与气速（Ｕｇ）、液速（Ｕｌ）和磁场强度（Ｈ）的经验关联式．关联式如下：     

氟利昂体系汽液平衡二元相互作用参数的普遍化关联

用ＭＨ（８１）方程关联了十一个氟利昂体系的等温汽液平衡数据，得出其二元相互作用参数，关联结果同实验符合良好。根据分子热力学的基本原理，加上一些经验的关联，提出了一个四常数的关联式来关联氟利昂混合物的ＭＨ（８１）方程二元相互作用参数，利用关联结果推算了ＤＭＥ／Ｒ１５２ａ体系在２８３．３１Ｋ、２９３．８４Ｋ、Ｒ２３／Ｒ２２在２５８．１５Ｋ和Ｒ３２、Ｒ１５２ａ在２７３．１５Ｋ的等温汽液平衡，与实验数据进行对照吻合良好，表明此式有相当程度的预测性，在氟利昂替代物的预选和工程计算中有重要的实际应用价值。     

含CO_2体系高压相平衡测定和关联

测定了ＣＯ２－Ｃ２Ｈ５ＯＨ和ＣＯ２－Ｈ２Ｏ体系的高压汽液平衡数据，并采用ＥＯＳ／ＧＥ模型推导出局部组成混合规则，用ＳＲＫ方程关联结果与实验值符合较好。     

用SRK状态方程计算二氧化碳在N-甲基二乙醇胺水溶液中的溶解度

本文对二氧化碳在Ｎ－甲基二乙醇胺水溶液中的溶解度数据进行了收集和评估,并用ＳＲＫ状态方程对文献数据进行了关联计算。结果表明本模型对二氧化碳溶解度的计算精度与实验的测定精度相当。可用于过程的模拟计算。     

超临界二氧化碳在非常规油气藏开采中的应用研究

超临界二氧化碳具有接近于气体的低黏度和高扩散系数,又具有接近于液体的高密度,这些性质引起了国内外石油行业的广泛关注,并将其引入油气藏开发。研究结果显示,超临界二氧化碳非常适合应用在非常规油气藏的开采作业中。我国的非常规油气藏储量丰富,但采收率普遍较低,将超临界二氧化碳引入非常规油气藏的开发很有必要。本文分析了超临界二氧化碳在非常规油气藏开采中的钻井、压裂、驱油及除垢洗井等作业过程中的技术原理和特点,认为,超临界二氧化碳弥补了水基钻井液或压裂液的不足,提高了效率,减少了污染,适用性好,并总结了超临界二氧化碳在非常规油气藏中的未来发展和总体优势。     

超临界二氧化碳干气密封相态分布规律与密封性能研究

以超临界二氧化碳干气密封为研究对象，分别以维里方程、Lucas方程描述二氧化碳真实气体效应、黏度的变化，在考虑阻塞流效应的同时，采用有限差分法对考虑离心惯性力效应的Reynolds方程与能量控制方程进行耦合求解，分析讨论了工况参数与槽形结构参数对其相态分布规律与密封性能的影响。研究表明：S-CO₂从密封端面进口至出口的流动过程中，如果工况参数设置合理，将由超临界态逐渐转变为气态，并不会出现液态；较低的进口压力、进口温度以及转速，均会容易导致潜在的凝结流动发生；相比于工况参数对相态分布的影响，槽形参数对相态分布的影响较小，近乎可以忽略；开启力除了随进口温度的升高而减小外，均随进口压力、转速、槽深、螺旋角的增大而增大；泄漏率随进口温度和转速的增大而减小，但其随进口压力、槽深、螺旋角的增大而增大。这些结果为进一步研究超临界二氧化碳干气密封提供了一定的支撑。     

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.     

缔合模型用于超临界萃取溶解度计算

基于在超临界萃取过程中,同时存在超临界流体相－固相相平衡和超临界相缔合反应平衡的假设,提出一一个用于超临界萃取溶解度计算的缔合模型。该模型式用于２７个固体溶质和５个液体溶质在超临界溶剂中溶解度的计算,其平均相对偏差绝大多数体系均小于１０％。     

Evaluation of density-based models for the solubility of solids in supercritical carbon dioxide and formulation of a new model

Many models have been developed to calculate supercritical solubility behavior and most can be either a semi-empirical relationship or based on an equation of state. In this work, density-based, semi-empirical models were evaluated in terms of their ability to accurately correlate solid solubility in supercritical carbon dioxide. The models considered were the methods of Chrastil, del Valle and Aguilera, Adachi and Lu, Méndez-Santiago and Teja, and Bartle. Six binary systems (solid + supercritical carbon dioxide), each with three isotherms, were selected for this evaluation. The average error was calculated for all 18 isotherms with each of the models evaluated. The solid compounds used in this study were naphthalene, anthracene, fluorene, hydroquinone, 1,5-naphthalenediamine, and cholesterol. The solubility data were obtained from literature. Of the previously mentioned models, the Adachi-Lu and del Valle-Aguilera equations provided, in general, lower average error than the other models. Since the Adachi-Lu equation and the del Valle-Aguilera equation correct for different effects, a new model is proposed in this work as a combination of the previous two methods. The proposed equation provided the least overall average error compared to all other models considered in this study. The new model is particularly useful when the reduced density of the solvent is below 1 where previous models tend to fail. This work also emphasizes on the advantages of expressing density-based models in dimensionless form to avoid dimensional inconsistencies in Chrastil-type models. One of the benefits, for example, is that parameters obtained by different authors can be readily compared, regardless of the units used.     

Prediction of Solubility of Cholesterol in Supercritical Solvents

In this study the solubility of cholesterol was calculated in two supercritical pure solvents (carbon dioxide and ethane) as binary systems, and four supercritical solvent/co-solvent systems as ternary systems (cholesterol/carbon dioxide/methanol, cholesterol/ethane/acetone, cholesterol/ethane/hexane, cholesterol/ethane/propane) in various temperatures by SRK, PR, and SAFT equations of state. Pure molecular parameters of SAFT equation of state were obtained by fitting vapor pressure and liquid density data. Also the molecular parameters of cholesterol were obtained by fitting the solubility data of binary systems in one temperature, then they were used for the same system in other temperatures and for ternary systems with the same solvent. Results show that the SAFT equation of state can predict the trend and amount solubility of cholesterol in supercritical solvents much better than the other equations of state.     

Comminution of pharmaceutical substances by the adiabatic expansion of supercritical fluid solutions

The adiabatic expansion of supercritical fluid solutions and solubility in pharmaceutical substance–carbon dioxide systems have been investigated. The solubility and average particle size of pharmaceutical substances depend on thermodynamic and geometric parameters of the process. Experimental data on the solubility of pharmaceutical substances in supercritical carbon dioxide have been gained, and empirical binary molecular interaction parameters for the Peng–Robinson equation have been derived. A numerical solution has been obtained for the unified model of nucleation and particle growth (in the drop theory approximation) in the expansion of a steady-state, two-dimensional, viscous, axisymmetric, compressible, supercritical carbon dioxide–pharmaceutical substance flow in a channel with a constant cross section and in a free jet. The correlation parameter of the condensation function, which characterizes the particle growth kinetics, has been determined.     

PREDICTION OF MOLAR VOLUMES, VAPOR PRESSURES AND SUPERCRITICAL SOLUBILITIES OF ALKANES BY EQUATIONS OF STATE

A generalized cubic equation of state which can represent all the cubic equations is introduced and thermodynamic property relations for it are presented. Five cubic equations of states with respective mixing rules are used to predict molar volumes and vapor pressures of pure alkanes (from methane till n-tritriacontane) and solubilities of solid wax components (high molecular weight alkanes) in supercritical solvents. They are the RK (Redlich-Kwong), MMM (Mohsennia-Modarress-Mansoori), RM (Riazi-Mansoori), PR (Peng-Robinson), and SRK (Soave-Redlich-Kwon) equations of state. The experimental data necessary to compare the equations of state are taken from the literature. It is demonstrated that the SRK equation of state is more accurate for predicting vapor pressures of alkanes. The RM equation of state is shown to be more accurate for predicting molar volumes of saturated and sub-cooled liquid alkanes as well as molar volumes of alkanes in their supercritical condition. For the solubility of wax components in supercritical solvents it is shown that the MMM equation of state gives the least AAD% for the 270 data points of 10 binary systems studied consisting of a high molecular weight alkane and supercritical ethane and carbon dioxide.     

超临界二氧化碳介入的α-松油醇催化合成1，8-桉叶素

提出超临界二氧化碳介入α-松油醇异构合成1,8-桉叶素的方法,并采用二极管阵列检测器测量超临界二氧化碳下α-松油醇/环己烷体系的最大吸收波长研究二氧化碳加入量与极性的关系。考察了溶剂体系极性、溶剂量和二氧化碳压力对磷钨酸/聚离子液体（PW/PIL）催化剂催化α-松油醇异构合成1,8-桉叶素的影响,并探讨了超临界二氧化碳介质中,PW/PIL催化剂催化α-松油醇异构合成1,8-桉叶素可能的反应机理。开发了一种绿色高效的1,8-桉叶素合成工艺,当环己烷/α-松油醇的质量比10∶1,PW/PIL催化剂/α-松油醇的摩尔比0.0163∶1,CO₂压力19.0 MPa,50℃反应8 h时,α-松油醇的转化率为89.3%,1,8-桉叶素的选择性为54.6%。研究表明,超临界二氧化碳起到共溶剂、膨胀溶剂、降低溶剂体系极性的三重作用,从而改善了催化剂的团聚现象,提高了1,8-桉叶素的选择性。     

立方扰动硬链方程

本文通过在SPHC方程中引入拟合Carnahan-Starling硬球方程所得的斥力项,建立了立方型扰动硬链状态方程.由拟合正构烷烃的饱和蒸汽压和液相密度所确定的3个纯组分参数与碳原子数呈良好线性关系.对19种纯物质饱和蒸汽压和液相密度数据计算的平均相对误差分别为1.52%和2.97%;对混合物提出了一种新的混合规则,应用于预测含短链和长链烃类及二氧化碳、硫化氢混合物的高压汽液平衡,优于采用SPHC、SRK和PT方程所得的计算结果.     

丙烷-乙醇-水体系相平衡研究

提出了改进的DDLC-MH(81)状态方程,用于丙烷-乙醇-水体系二元汽液平衡数据的关联计算,其模型参数与温度有良好的线性关系.并用汽相循环法测定了该体系在不同温度下的二元及三元VLE数据,结果与模型的推算值取得良好的一致.并用模型预测了超临界丙烷条件下的三元相平衡数据.结果表明,在液相乙醇浓度高于0.2的情况下,超临界丙烷比超临界二氧化碳有更高的乙醇溶解度和选择性.