溴化锂及离子液体水溶液密度、黏度和表面张力测定与计算

常压条件下,实验测定了不同温度（283.15~343.15 K）下吸收制冷/热泵工质对——溴化锂（LiBr）、1-乙基-3-甲基咪唑醋酸盐（[EMIM][OAC]）和1-丁基-3-甲基咪唑硫氰酸盐（[BMIM][SCN]）水溶液的密度、黏度和表面张力,借助线性方程和Vogel-Tammann-Fulcher（VTF）模型,分别成功关联了密度和黏度实验值。研究结果表明：在相同条件下,溴化锂水溶液的密度大于离子液体水溶液的密度,而前者的黏度小于后者;对表面张力,随着溴化锂含量增加,其水溶液的表面张力值增加,而少量离子液体可使水的表面张力快速下降。根据实验黏度和表面张力分别获得了能量势垒和表面熵/焓,表明各水溶液中分子或离子迁移难易程度遵循[EMIM][OAC] > [BMIM][SCN] > LiBr,表面有序性遵循[BMIM][SCN] > [EMIM][OAC] > LiBr。研究结果可为吸收制冷/热泵工质对及低温余热回收系统的设计和计算提供可靠的数据支撑。     

气液界面对流传质的观测与定量分析

采用光学纹影系统对乙醇和水双组分解吸传质过程的对流结构的界面湍动进行了定性观察和定量分析。建立了一套水平非稳态气液传质设备,试验观测了乙醇和水体系中液相组分向气相传质过程的Marangoni界面对流结构。还通过对传统纹影方法的改进,对乙醇解吸传质过程的浓度(本文用质量分数表示)梯度场进行了定量测量。定量分析表明乙醇和水系统解吸过程中,引发界面湍动的原因是局部较大的表面张力梯度。定量分析的结果很好的解释了伴随Marangoni效应的传质过程的混乱的对流结构,为进一步对界面湍动现象的分析提供了帮助。     

LiCl溶液垂直管外降膜发生效果的实验

为了探究LiCl水溶液在低位太阳能吸收式制冷系统中的发生过程中的传热传质效果,在降膜发生实验装置基础上研究了LiCl水溶液在垂直管外降膜发生的传热传质过程。阐述了不同运行工况如不同的热水和溶液的流量、热源的温度、溶液的浓度和系统压力对LiCl水溶液发生过程传热传质效果的影响。同时也进行了相同工况下LiBr水溶液的对比实验。结果表明相同运行工况下LiCl水溶液降膜发生过程和LiBr水溶液的降膜发生过程有着相似的变化规律。虽然LiCl水溶液的垂直降膜发生速率略低于LiBr水溶液,但传质效果相差不大,LiCl溶液的低运行浓度有利于循环热力性能的提升。     

Effect of interfacial velocity and interfacial tension gradient on momentum,heat and mass transfer

The effect of interfacial velocity and interfacial tension gradient on momentum, heat and mass transfer was studied theoretically. After reviewing current knowledge regarding interfacial velocity effects, the interfacial tension gradient effect is discussed as a numerical solution of the laminar boundary layer equations. The enhancement and suppression of interfacial mobility, and the rates of interphase momentum, heat and mass transfer were related to the Marangoni number. A diagram showing the effect of interfacial tension gradient on momentum, heat and mass transfer is presented.     

高效传热管的实验研究

建立了样机型模块式溴化锂吸收式制冷机高效传热管试验台;对研制成功的高效传热管在接近工业条件下进行了传热传质性能和添加表面活性剂影响的实验研究,提供了可供工程设计使用的关联式,并观察了马拉哥尼对流.实验研究表明,只有将有关技术参数如喷淋密度、冷却水和冷媒水流速等设计在合适的范围内,高效传热管才能取得较好的强化效果;吸收器高效管必须添加适量的表面活性剂,才能获得最佳传热传质效果.使用本文的高效传热管可使一台1160 kW的溴化锂吸收式制冷机节省铜材1700～2000 kg,质量减轻30%～40%.     

MARANGONI AND ELECTRIC FIELD EFFECTS UPON MASS TRANSFER TO TRANSLATING DROPS

Interfacial stresses arising from the transfer of an interfacial tension-lowering solute (Marangoni effects) or the presence of an electric field may significantly alter the interfacial velocity of a moving droplet with consequent effects upon the rate of convective mass exchange between the drop and the external medium. The present theoretical study considers separately the Marangoni and electric field effects and delineates the conditions under which mass transfer enhancement should be observed. For Peclet numbers in the range of 10-100, enchancement is predicted for a Marangoni to Peclei number ratio of 100 or for a dimensionless electric velocity of 0.1, As an example, numerical results for a Peclet number of 50 indicate an increase of approximately 20% in the mass transfer coefficient for either a Marangoni number of 5000 or a dimensionless electric velocity of 0.5 for phases of comparable transport properties and solute solubilities.     

膜蓄能器放能过程的传热传质特性分析

膜构架蓄能器是以中空纤维膜为基本结构,不仅能够实现蓄能,同时能够解决溴化锂溶液浓度差蓄能器中结晶后的放能困难的问题。搭建了膜蓄能器放能过程传热传质实验测试系统,建立了应用于太阳能吸收式制冷系统中的膜架构蓄能器传热传质的三维数学模型,并利用 CFD 软件进行了求解。将计算结果与实验结果相比较,验证了该三维非稳态数学模型的可靠性。实验和仿真结果表明,质量分数为70% 的溴化锂溶液的水蒸气分子平均传质速率比质量分数为60%的溶液高44.03%;当蒸发温度从4.5℃提高到12.3℃时,水蒸气分子的平均传质速率将提高108.34%;当膜通道的有效长度从80 mm减少到30 mm时,水蒸气分子的传质速率会提高40.77%。     

Drying-Induced Hierarchical Dimple Patterns on Partially Miscible Polymeric Films Under Ordered Convections

We describe the formation of hierarchical dual dimple patterns on polymeric sublayers by evaporation-induced interfacial stress. As water vapor condenses on partially miscible volatile sublayers, the resulting unstable wet-on-wet configurations trigger droplet assembly under ordered convection, giving rise to hexagonal traces of surface dimples, which coexist with highly ordered dimple arrays. Monitoring the time-dependent Marangoni numbers proved that the interfacial stress plays a crucial role in the transition between hierarchically and uniformly ordered dimple patterns.     

电解质溶液的受热降膜传热与Marangoni效应

采用红外热成像技术研究了电解质Na2SO4-H2O溶液受热降膜传热过程中的Marangoni效应。实验结果表明,降膜表面的流向和径向上存在分别由温度和浓度分布不均引起的热和溶质Marangoni效应。降膜径向热Marangoni效应引起了液膜的收缩,使液膜厚度增加,增大了液膜热阻;流向热Marangoni效应加剧了液膜的湍动,减小了液膜滞流层厚度,降低了液膜热阻;径向溶质Marangoni效应则减弱了热Marangoni效应对液膜的收缩作用,促进了液膜的扩展。分析发现在本实验条件下,表征Marangoni效应大小的Marangoni数Ma不能准确地反映不同雷诺数Re下Marangoni效应对降膜流动的影响,为此引入判断Marangoni效应对降膜流动影响程度的Marangoni效应影响因子ε,ε与实验结果具有较好的一致性。     

POOL BOILING OF BINARY MIXTURES

Nucleate pool boiling heat transfer coefficients for pure water, pure n-propanol and eight of their mixtures including the azeotrope were measured by using a horizontal electrically heated stainless steel tube of 3.35 mm O.D. and 9.8 cm long as heating element. This binary system was chosen for the reason that it is suitable for simultaneous investigation of the mass diffusion effect (the F effect), the effect of slowing down in bubble growth rate caused by the exhaustion of the volatile component near the vapor-liquid interface, the Marangoni effect (the M effect), the effect of surface tension gradient caused by the evaporation of the component of lower surface tension, and the dynamic surface effect (the Y effect), the effect of surface tension gradient caused by the stretching of vapor-liquid interface, on the boiling heat transfer rate in mixture. It is concluded that the mass diffusion effect can qualitatively account for the experimental results of the system. The discrepancy between the experimental data and the theoretical prediction by considering the F effect is due to taking no account of the intercorrelated effects of M and Y.

The effect of interfacial properties such as surface tension and contact angle on boiling heat transfer rate and the incipience of boiling were also evaluated.     

Effect of phase transfer catalysts on the interfacial tension of water/toluene system

The effect on the interfacial tension of the water toluene system has been studied at 25 °C in the presence of four phase-transfer catalysts i.e. tricaprylmethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, hex-adecytrimethyl ammonium bromide and hexadecyltributyl phosphonium bromide. The interfacial tension of aqueous phenol/resorcinol-toluene in the presence and absence of tricaprylmethyl ammonium chloride has also been reported. Attempt has been made to elucidate the change in volumetric rate of extraction with different catalysts for two phase reactions, on the basis of interfacial tension.     

Interfacial turbulence accompanying chemical absorption

Absorption rates for carbon dioxide into aqueous solutions of EDA and MEA with and without adding surface active agent were measured in a laminar liquid-jet apparatus to check and verify the Marangoni effect. In addition, experiments were conducted for the tracer desorption of ethylene from aqueous EDA and MEA solutions into carbon dioxide or nitrogen stream. It has been concluded that the Marangoni effect cannot be neglected for such short contact times as in a laminar liquid-jet. The Marangoni instability accompanying the present chemical absorptions is attributed to combinated effects of the presence of ionic products, the depletion of the reactant liquid near the interface and an increase in interfacial temperature.     

氨-水-溴化锂三元工质氨吸收式制冷性能

通过试验研究了使用氨-水-溴化锂三元工质对氨吸收式制冷性能的影响。根据现有研究,工质中溴化锂的质量分数设定为5%、10%、15%和20%,试验中发生温度设定为90～130℃,蒸发温度设定为-19～-4℃,冷却水温度设定为22～33℃。通过试验发现,溴化锂质量分数在15%时对COP提升效果最好,发生温度在130℃时性能系数可以达到0.408,蒸发温度在-4℃时性能系数可达0.410,冷却水温度在22℃时性能系数可以达到0.412;而且添加三元工质可以减小精馏能耗且充分利用低品位热能,因此采用氨-水-溴化锂三元工质可以在高效利用热能情况下改善氨吸收式制冷系统的劣势。     

Transient rise velocity and mass transfer of a single drop with interfacial instabilities - experimental investigations

An experimental study of transient drop rise velocities and mass transfer rates was carried out in the system toluene/acetone/water which is known to show interfacial instabilities. The rise velocity of toluene drops was studied without added solute (acetone) in the diameter range 1-3 mm and with added solute for 2 mm drops. The initial concentration of the transferred solute was varied from 0 to 30 g/L. The transient drop rise velocities were used to quantify the Marangoni effect since the drag coefficient depends on the strength of the Marangoni convection patterns caused by interfacial tension gradients. In addition, mass transfer measurements were carried out in order to determine the modification of the mass transfer rate due to Marangoni convection. Velocity and mass transfer measurements were then correlated via the contact time. Results reveal the existence of a range in which a critical value for the solute concentration can be defined for Marangoni convection.     

气液界面Marangoni效应对传质系数的影响

在气液相际传质过程中,界面Marangoni湍动会对传质过程产生重要的影响,为此,建立了一套气液接触传质设备,以使得通过N2与异丙醇稀溶液逆流接触将液体中使表面张力降低的溶质解吸出来,从而引发Marangoni湍动,提高传质速率。发生Marangoni对流时,液相的传质系数比只依靠扩散传质而不考虑Marangoni效应时大,因此引出增强因子F这一概念,通过计算F的值即可判断Marangoni效应对传质速率影响的程度。提出了一个包括Marangoni准数的计算传质系数关联式,其计算结果与实验结果相符．     

Surface-tension-induced interfacial convection and its effect on rates of mass transfer

Surface-tension-induced interfacial convection (Marangoni phenomena) can appear as a result of mass and heat transfer, compression and dilatation of surface films or their non-Newtonian behaviour and owing to presence in the interface of electrostatic charges. In process engineering problems the mass transfer effect is usually predominant and, depending on the geometry of the system, leads to surface renewal or changes in interfacial area. The surface renewal phenomena can appear as instabilities or disturbances and their effect on mass transfer is presented for transfer to and from drops as well as across flat interfaces in stirred and laminar flow contactors. Mass transfer coefficients and drag coefficients of drops are compared under conditions of undisturbed (diffusional) transfer, cellular convection and interfacial turbulence for stable and unstable direction of transfer. The importance of gravitational instability is indicated.     

红外热像法研究降膜流动

采用高精度红外热成像技术研究固体平壁上加热和冷却液膜流动性能,比较了不同加热强度下液膜表面的温度场特征以及加热温差对固壁上液体分布的影响。传递过程中,界面上浓度和温度变化引起的表面张力梯度,驱使低界面张力处的液体流向高界面张力处（Marangoni效应）,从而造成了液体特殊的流动现象与分布特征。在受热/冷却降膜过程中,由于流速和传热的差异,液膜表面存在一定的温度梯度。横向的温度梯度远大于流动方向的温度梯度,引起的Marangoni效应会造成受热液膜收缩和冷却液膜扩展,从而明显地影响液膜的相界面积及其传递性能。     

相间传质对气泡聚并过程影响的实验研究

设计了一套双气泡聚并实验系统,考察了相间传质对气泡聚并过程的影响,气相采用非相变的N2,液相为挥发性的丙酮和乙醇水溶液. 利用该系统测定了25~50℃温度下,不同组分浓度、鼓泡频率和气泡直径时气泡的聚并特性. 结果表明,相间传质诱导的Marangoni效应使聚并时间随温度升高呈先减小后增大的趋势,聚并时间的分散性在较高温度下显著增大,采用聚并效率描述气泡聚并特性更合适;聚并效率在温度升高到一定程度后开始降低并趋于最小值,该值随溶液浓度增加而减小,稳定因子可定量描述Marangoni效应;鼓泡速率和气泡直径增加1倍,最小聚并效率分别减小50%和67%.     

基于氯化钙溶液的混合盐溶液除湿剂物性测量

为了改善单一除湿盐溶液的性能,同时降低耗费成本,越来越多的学者致力于混合除湿盐溶液的研究。考虑以价格低廉但除湿效果一般的氯化钙溶液为基础溶液,添加氯化锂或溴化锂颗粒形成混合溶液来提高单一氯化钙溶液的除湿能力。测量了单一氯化钙溶液,加LiCl/LiBr颗粒后饱和混合溶液的质量浓度,探究极限溶解度,其次对氯化钙、氯化锂不同配比混合溶液在不同温度下的黏度及表面张力进行了测量。通过溶解度的实验测量,发现已经饱和的氯化钙溶液中还可继续溶解最高达8%的LiCl/LiBr晶体。测量得不同配比氯化锂、氯化钙混合溶液的黏度与表面张力值,通过比较发现氯化锂与氯化钙1：1的质量比下,混合溶液的黏度与表面张力均最低。     

Thermodynamic and Surface Properties of Aqueous 1-Dodecyl-3-Methylimidazolium Chloride [C12mim][Cl] Solution in the Presence of a Series of Inorganic Salts

The micellization behavior of amphiphiles is a well-analyzed physicochemical phenomenon, which can be easily influenced by various parameters such as pressure, temperature, and the presence of different additives. Inorganic salts are able to affect the thermodynamic and surface properties of amphiphiles significantly. The effect of a series of salts as additives namely lithium chloride (LiCl), potassium chloride (KCl), sodium chloride (NaCl), sodium bromide (NaBr), and sodium iodide (NaI) on interfacial chemical characteristics of the surface-active ionic liquid (SAIL) 1-dodecyl-3-methylimidazolium chloride [C₁₂mim][Cl] in aqueous solution were examined through conductance, surface tension, fluorescence, ¹H NMR, and dynamic light scattering measurements. The interfacial and thermodynamic parameters of all investigated SAIL-salt systems were evaluated from surface tension and conductance measurements, respectively. A detailed analysis of the microenvironment of the micelles and the size of the micelles was done using ¹H NMR and dynamic light scattering measurements.