超临界流体结晶技术研究进展

综述了超临界流体结晶技术的理论和应用进展，重点介绍了三种超临界流体结晶技术：超临界溶液快速膨胀结晶法，超临界流体抗溶剂结晶法和超临界流体梯度结晶分离法，并指出了它们的研究方向。     

超临界流体制备超微粉体的研究进展

超临界流体制备超微粉体是一项新技术，利用超临界流体较好的溶解、扩散和传输能力，能制备出高质量的超微粉体，根据其工艺原理可分为：超临界流体快速膨胀法（RESS），超临界流体脱溶剂法（GAS）和超临界流体微乳法，本文对RESS，GAS和超临界流体微乳法制备超微粉体的原理进行了总结，并对这3种方法在食品、医药、化工材料等领域中的研究现状进行了介绍。     

超临界流体干燥技术在纳米粉体制备中的应用

由于纳米粒子的表面效应，用传统的干燥方法干燥纳米粉体时极可能产生团聚结构。超临界流体干燥技术是制备具有高比表面积、孔体积、较低密度和低热导率的块状气凝胶和纳米粉体的重要途径之一。介绍了超临界流体的性质、超临界流体干燥技术的研究进展、超临界流体干燥的工艺与设备及过程的影响因素，阐述了超临界流体干燥技术在纳米材料制备中的应用，并指出了超临界流体干燥过程的控制技术及注意点，为进一步加强超临界流体干燥技术的理论研究和拓展超临界流体干燥技术的应用领域奠定了基础。     

基于低温制冷机的流体液化与凝固过程可视化装置

液化和凝固是流体系统工程中常见的两种基本现象。由于低温流体液化点和凝固点温度都非常低，给受控条件下观测流体的液化和凝固过程带来了困难。设计并搭建了基于G-M低温制冷机的流体受控液化和凝固过程可视化实验装置，并对氮气（44~80 K）、氩气（50~90 K）、氧气（50~90 K）3种低温流体的液化和凝固过程进行控制观测，获得了3种流体在一定温度下的相变过程的视频图像。实验结果表明，3种低温流体的凝固过程表现出较明显的固化行为特性差异。     

流动模型方法及其在化工中的应用

THEMETHODANDUSEOFFLOWMODELINCHEMICALENGINEERING1前言当流体流过化工设备时，由于流体与器壁和流体微元（分子或分子团）间的相互摩擦，各流体微元通过设备的停留时间会不同，这种具有不同停留时间流体微元间的混合叫做返混。流体返混合影响到设备的传热、传质和反应的结果。目前，在化学工程研究和设计领域中，一般是采用流动模型方法来处理和解决这一问题。目前，流动模型方法广泛用于反应器、换热器、蒸馏塔板、填料塔等化工设备的模拟计算，它为这些设备的设计、分析、操作及过程调优发挥了重要作用。但是，由于…     

如何降低机泵泄漏率

在石油及天然气的储存和运输中，广泛的使用各种管输流体机械，用来增加流体能量，克服流体阻力，达到沿管路输送的目的。泵的运行状况直接影响产品质量和装置平稳运行，对于正常生产影响较大。     

超临界流体技术及其在生物工程中的应用

介绍了在生物工程有着广泛的应用前景的多种超临界流体技术，包括提取生物活性物质的超临界流体萃取，超临界条件二氧化碳中制备手性药物制备和淀粉水解制取葡萄糖的非水酶催化反应，超临界水条件下纤维素水解制备葡萄糖，超临界流体中的细胞破碎，制备缓释药物和色说载体的超临界流体溶液快速膨胀和气体抗溶剂结晶和沉淀技术。     

超临界流体改质煤焦油研究进展

中国是一个多煤少油的国家，煤制油技术在我国有着广泛的应用前景。由于超临界流体对有机物有较好的溶解性，因此越来越多地应用到煤焦油深加工过程中。本文总结了超临界流体改质煤焦油过程中，操作参数对煤焦油轻质化的影响和强化改质方法，重点分析了超临界水和超临界甲醇，超临界水改质煤焦油主要体现在物理上的溶解和分散作用，而超临界甲醇除此之外，有一定的供氢能力，可以为反应提供氢，但是供氢能力有限。因此，本文又讨论了添加催化剂、自由基引发剂、加氢等手段强化超临界流体改质煤焦油。在此基础上对超临界流体改质煤焦油进行了展望，将超临界流体的萃取和超临界改质耦合在一起，充分发挥超临界流体优越性；选择新的超临界流体、催化剂等促进煤焦油轻质化。     

液-液两相流体黏度对微通道内流型的影响

为了研究流体黏度对液-液两相流流型的影响，采用实验和数值模拟相结合的方法,研究十字型微通道内液-液两相流流型变化。结果表明，当两相流体系中存在高黏度流体时，会加剧两相界面的不稳定性，两相流流型极易向不规则流和环状流转换，且当连续相流体黏度较高时，液滴的形状更易为子弹流。通过引入毛细数和韦伯数，提出两相流流型转换关系。当连续相流体和分散相流体分别由水平通道和垂直通道流入时，通过合理调节两相流体流速，可在微通道下游实现大小液滴的融合。这一方式将为高黏度流体流动操控提供新思路，通过控制两相流速，可以实现不依赖于复杂微通道结构的液滴被动融合。     

超临界CO2流体萃取装置的污染分析与控制

针对超临界CO2流体萃取装置的工艺特点，分析了超临界CO2流体萃取装置中主要污染物的组成种类及其主要来源，指出噪声是超临界CO2流体萃取装置的主要污染物，同时提出从污染源着手，控制和减少超临界CO2流体萃取装置污染的一些措施。     

Extension to mixtures of two robust hard‐sphere equations of state satisfying the ordered close‐packed limit

Two new hard‐sphere EOS are proposed and tested using the same attractive potential terms used by the SAFT EOS. Generalized expressions for the pair RDF at contact value, the compressibility factor, and the excess chemical potentials have been derived. Extension to mixtures is tested using three mixing rules for multicomponent hard‐sphere fluids. The proposed EOS combined with the Santos et al. and the Barrio‐Solana mixing rules reproduced the compressibility factors and the excess chemical potentials more accurately than the Boublik‐Mansoori‐Camahan‐Starling‐Leland (BMCSL) EOS. However the pair RDF at contact value had larger deviations than those obtained with the BMCSL EOS. The combination of the proposed equations and the Barrio‐Solana mixing rule gave an accurate reproduction of the compressibility factor for binary hard‐sphere fluids with high diameter ratio even in the low concentration regions of the larger spheres.     

SIMPLIFIED HARD-SPHERE AND HARD-SPHERE CHAIN EQUATIONS OF STATE FOR ENGINEERING APPLICATIONS

A simple hard-sphere equation of state is proposed. This hard-sphere equation is a ratio of second-order polynomials that meets the ideal gas and close-packed density limits. It predicts the compressibility of hard-sphere fluids at low and medium densities to within a degree of quality similar to the widely used Carnahan-Starling equation. In addition, the proposed equation performs better at high densities, particularly near the close-packed density. An expression is also derived to relate the site-site correlation function at contact for hard dimers with the site-site correlation function at contact for hard spheres. With this relationship, the thermodynamic perturbation-dimer theory (TPT-D) of hard-sphere chains is simplified. The new theory performs comparably with the TPT-D when the compressibility factors of hard-sphere chain fluids containing up to 201-mer are predicted, however, it has the advantages of both simplicity and accuracy. From a practical perspective, this theory can be used to construct equations of state for polymer solutions or fluid systems containing short- and long-chain molecules.     

SIMPLIFIED HARD-SPHERE AND HARD-SPHERE CHAIN EQUATIONS OF STATE FOR ENGINEERING APPLICATIONS

A simple hard-sphere equation of state is proposed. This hard-sphere equation is a ratio of second-order polynomials that meets the ideal gas and close-packed density limits. It predicts the compressibility of hard-sphere fluids at low and medium densities to within a degree of quality similar to the widely used Carnahan-Starling equation. In addition, the proposed equation performs better at high densities, particularly near the close-packed density. An expression is also derived to relate the site-site correlation function at contact for hard dimers with the site-site correlation function at contact for hard spheres. With this relationship, the thermodynamic perturbation-dimer theory (TPT-D) of hard-sphere chains is simplified. The new theory performs comparably with the TPT-D when the compressibility factors of hard-sphere chain fluids containing up to 201-mer are predicted, however, it has the advantages of both simplicity and accuracy. From a practical perspective, this theory can be used to construct equations of state for polymer solutions or fluid systems containing short- and long-chain molecules.     

Twenty‐one new theoretically based cubic equations of state for athermal hard‐sphere chain pure fluids and mixtures

Eight new hard‐sphere equations of state (EOS's) were obtained from molecular simulation data for the pair correlation function g_HS(σ) vs. packing fraction η and combined with three theoretical schemes to obtain 21 new cubic EOS's for athermal hard‐sphere chains (AHSC's). The eight new hard‐sphere EOS models successfully reproduced isotropic fluid compressibility factor Z_HS and g_HS(σ) vs. η simulation data and predicted metastable liquid Z_HS vs. η and virial coefficients up through B₁₀. Moreover, calculated Z vs. η and reduced second‐virial coefficient vs. chain length m were compared with molecular simulation data for chains up to m = 201 for a set of representative (eight of twenty‐one) chain equations. Z vs. η for three AHSC binary mixtures was also successfully predicted. The results indicate that the new cubic EOS's give a satisfactory representation of simulation data for chain fluids and can be used to develop theoretically based cubic EOS's for “real” fluids including attractive effects. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1677–1690, 2015     

硬球链流体在平板和硬球表面分布的密度泛函理论

采用Yethiraj和Woodward的密度泛函理论方法,结合胡英和刘洪来等发展的硬球链流体状态方程,得到了自由连接硬球链流体在平板狭缝中和球形固体颗粒表面附近的密度分布表达式,并计算了在两平行壁所组成的狭缝中和直径大小不同的球形固体颗粒周围硬球链分子的链节密度分布.理论计算结果与作者采用Dickman 和Hall 的方法进行Monte Carlo计算机模拟结果非常吻合.颗粒直径对链状分子的密度分布有一定的影响,随着固体颗粒直径的增加,靠近颗粒表面附近的链节密度降低.     

实际流体的微扰理论状态方程研究

在微扰理论和硬球链状态方程基础上,对链状分子间中的氢键作用采用了一种新的处理方法,提出一个新的三参数的实际流体状态方程。将此方程用于关联３３个纯液体的饱和蒸汽压和液体密度,并由所得到的参数预测了汽相的密度。此状态方程比ＡＰＡＣＴ和ＳＡＦＴ状态方程简单,而计算的精确度则相当     

用微扰理论研究链状流体的状态方程

本文用微扰理论建立了链状流体的分子热力学模型，并给出了体系Ｈｅｌｍｈｏｌｔｚ自由能函数及状态方程的表达式。对非极性流体，体系的热力学性质由硬球作用、成链作用及色散作用三部分组成。对极性链状流体，分子间作用还包括偶极作用及诱导作用。将此模型应用于正烷烃及正一元醇的计算，同时关联纯液体的密度和饱和蒸汽压，结果与实验值符合良好。本文中所用的参数具有明确的物理意义。与前人的工作相比较，本文理论处理简单并且有一定的计算精度     

含临界点的统计缔合流体理论研究(Ⅰ)非极性流体

从适合于临界点的计算出发 ,对统计缔合流体理论方程进行改进 :(1)对链状分子的每个链节考虑其非球形度 ;(2 )提出必须考虑链节成链时对色散作用的影响 .建立了扩展的统计缔合流体理论状态方程 ,对于正构烷烃和异构烷烃的计算表明 ,该方程计算温度范围大 ,从低温区到临界区 ,特别是在临界点附近精度有明显提高 ,临界点的计算值和实验值基本符合 .扩展了理论状态方程的适用性 ,可望用于各种含临界区域流体体系的热力学计算     

Development of the semi-empirical equation of state for square-well chain fluid based on the Statistical Associating Fluid Theory (SAFT)

A semi-empirical equation of state for the freely jointed square-well chain fluid is developed. This equation of state is based on Wertheim’s thermodynamic perturbation theory (TPT) and the statistical associating fluid theory (SAFT). The compressibility factor and radial distribution function of square-well monomer are obtained from Monte Carlo simulations. These results are correlated using density expansion. In developing the equation of state the exact analytical expressions are adopted for the second and third virial coefficients for the compressibility factor and the first two terms of the radial distribution function, while the higher order coefficients are determined from regression using the simulation data. In the limit of infinite temperature, the present equation of state and the expression for the radial distribution function are represented by the Carnahan-Starling equation of state. This semi-empirical equation of state gives at least comparable accuracy with other empirical equation of state for the square-well monomer fluid. With the new SAFT equation of state from the accurate expressions for the monomer reference and covalent terms, we compare the prediction of the equation of state to the simulation results for the compressibility factor and radial distribution function of the square-well monomer and chain fluids. The predicted compressibility factors for square well chains are found to be in a good agreement with simulation data. The high accuracy of the present equation of state is ascribed to the fact that rigorous simulation results for the reference fluid are used, especially at low temperatures and low densities. This paper was presented at the 8th APCChE (Asia Pacific Confederation of Chemical Engineering) Congress held at Seoul between August 16 and 19, 1999.     

Improving the simplified‐perturbed‐hard‐chain theory equation of state using a new non‐attracting hard‐sphere equation

In this research a new simple non‐attracting hard‐sphere equation is introduced. The equation meets the ideal gas and close‐packed limits and is in accordance with computer simulation data with reasonable accuracy. When this equation is used with the simpli‐fied‐perturbed‐hard‐chain theory equation of state, improvements on the calculation of vapour pressure and saturated liquid density of pure compounds are observed. For 35 pure compounds of different classes, the averages of absolute error are 3.31% and 4.20% for the calculation of vapour pressure and saturated liquid density, respectively. The respected errors for the original equation of state are 3.53% and 4.96%, respectively. Moreover, the use of the new hard‐sphere equation in place of the Carnahan‐Starling equation in the simplified‐perturbed‐hard‐chain theory equation of state, does not have any appreciable effect on the prediction of K factors in VLE calculations.