水杨酸苯酯与C4醇固液平衡测定与关联

In an equilibrium vessel,the solid-liquid equilibria(SLE) for three binary mixtures of phenyl salicylate with 1-butanol,2-butanol,and 2-methyl-1-propanol,respectively,have been measured from 283.15 K to the melting temperature of the solute using a method in which an excess amount of solute was equilibrated with the alcohol solution.The liquid concentrations of the investigated phenyl salicylate in the saturated solution were analyzed by UV spectrometry.Activity coefficients for phenyl salicylate have been calculated by means of the Wilson,NRTL,and UNIQUAC equations and with them were correlated solubility data that were compared with the experimental ones.The best correlation of the solubility data has been obtained by the Wilson equation by which the average root-mean-square deviation of temperature for the three systems is 1.03 K.     

Investigation of liquid–liquid equilibrium of the ternary system(water +1,6-diaminohexane + 2-methyl-1-propanol or 3-methyl-1-butanol) at different temperatures

In this study, the LLE data of ternary system (water+1,6-diaminohexane+2-methyl-1-propanol) and (water+1,6-diaminohexane+3-methyl-1-butanol) were measured at 293.15, 303.15 and 313.15 K under atmospheric pressure. Reliability of the experimental tie-line data was checked by empirical Hand, Othmer-Tobias and Bachman equations. Distribution coefficient (D) and selectivity (S) were calculated in order to investigate capability of the studied organic solvents for 1,6-diaminohexane extraction. The high values of separation factors demonstrated that 2-methyl-1-propanol and 3-methyl-1-butanol were applicable for this purpose. The experimental data were correlated by nonrandom two-liquid (NRTL) and universal quasi-chemical (UNIQUAC) models. The percent-root-mean-square deviation (RMSD) values for NRTL and UNIQUAC models were less than 0.15, which indicated that the experimental data have been sufficiently correlated.     

甲醇/H2O/H2O2/1,3,5-三甲苯/磷酸三辛酯五元系液液平衡的实验数据

测定了常压、 4 0℃下甲醇 /H₂ O/H₂ O₂ /1,3,5 -三甲苯 /磷酸三辛酯五元系液液平衡数据 ,分别用UNIQUAC模型和NRTL模型对实验数据进行了关联 ,取得了较满意的结果     

Salting-out effect of ionic liquids on isobaric vapor-liquid equilibrium of acetonitrile-water system☆

This paper presents the vapor–liquid equilibrium (VLE) data of acetonitrile–water system containing ionic liquids (ILs) at atmospheric pressure (101.3 kPa). Since ionic liquids dissociate into anions and cations, the VLE data for the acetonitrile+water+ILs systems are correlated by salt effect models, Furter model and improved Furter model. The overall average relative deviation of Furter model and improved Furter model is 5.43%and 4.68%, respectively. Thus the salt effect models are applicable for the correlation of IL containing systems. The salting-out effect theory can be used to explain the change of relative volatility of acetonitrile–water system.     

VAPOR-LIQUID EQUILIBRIA OF TOLUENE + n-BUTANOL AND TOLUENE + n-BUTANOL + CALCIUM CHLORIDE AT 94.0kPa

Vapor-liquid equilibrium data of toluene + n-butanol and toluene+ n-butanol + CaCl₂ (at saturation) were measured at a pressure of 94.0 kPa, using a modified Malanowski equilibrium still. The salt investigated in this work, i.e., CaCl₂, exhibits a slight salting-out effect on toluene. The experimental results of the salt-free binary were compared with those obtained from NRTL, ASOG, and UNIFAC models. The latter two models predicted the bubble-point temperatures within 0.5 K (as a root mean square deviation, RMSD) whereas the NRTL model, which was employed to establish thermodynamic consistency by directly fitting the experimental data, correlated the bubble-point temperatures with an RMSD of 0.2 K. On the other hand, the experimental data of toluene+n-butanol+CaCl₂ were compared with those predicted by the NRTL-Tan model for the effect of the electrolyte. This model predicted the bubble-point temperatures with an RMSD of 0.5 K. Calcium chloride has been shown not to have a sensible effect on the azeotropic composition.     

Analysis of equilibrium CO2 solubility and thermodynamic models for aqueous 1-(2-hydoxyethyl)-piperidine solution

1-(2-Hydoxyethyl)-piperidine (1-(2HE)-PP) is a new tertiary amine with desirable properties and can be potentially used to formulate superior absorbents for CO₂ capture. The equilibrium CO₂ solubility of 1-(2HE)-PP solution is measured over temperatures from 298 to 333 K, CO₂ partial pressures from 8.1 to 101.3 kPa and initial amine concentrations from 1 to 5 M. Two thermodynamic models, namely semiempirical model and activity coefficient model are developed for the system. The activity coefficient model shows better estimation solubility with an absolute average relative deviation (AARD) of 7.6%. In the comparison between the two models, a comprehensive analysis is presented. Some suggestions are provided for the similar model development. In addition, the speciation plot of CO₂ loaded 1-(2HE)-PP solution is predicted based on the activity coefficient model. The predictive pH values agree well with experimental data with AARD of 1.0%. Finally, the potential of 1-(2-HE)PP to be an alternative amine in CO₂ capture is evaluated.     

Vapor–liquid equilibria of HFC-161 + HFC-32 + DMF ternary mixture for low-grade heat driven absorption refrigeration system

Ternary mixture of fluoroethane (HFC-161) + difluoromethane (HFC-32) + N,N-dimethylformamide (DMF) is a promising working fluid for absorption refrigeration system which is an important energy saving technology receiving more and more attention. Investigation on vapor–liquid equilibrium (VLE) is necessary for further study and the application in absorption system of the ternary mixture. Therefore, an experimental system with continuous vapor-phase circulation is set up, measuring VLE data within temperature range of 283.15 to 323.15 K. The experimental data is correlated with Wilson and NRTL models, and BP-ANN method, respectively. The calculating data of Wilson model has the largest relative deviation of 5.14% and average relative deviation of 2.65% for vapor pressure, being the best one. The deviation of molar fraction data obtained with BP-ANN model has the best average relative deviation 3.07%. However, NRTL model provides a smooth predicted surface. The correlated parameters of the three models are given.     

莰烯+(+)-3-蒈烯体系汽液平衡数据的测定与关联

改进了Ellis平衡釜的保温、搅拌与压力控制系统，建立了一套可视窗口的实验装置。测定了莰烯+(+)-3-蒈烯体系在313.15、373.15和433.15 K下的汽液平衡数据；采用面积法和Van Ness检验法对实验数据进行热力学一致性检验，所有数据均符合Gibbs-Duhenm的热力学一致性；选用Aspen plus软件中NRTL、Wilson和UNIQUAC模型，由最大似然法对目标函数进行优化，实现对实验数据的关联。结果表明，气相组成和平衡压力的估算值与实验值的最大平均相对偏差为0.0128和0.0009，最大均方根偏差为0.0003和0.0012 kPa，相对挥发度的估算值与实验值的绝对平均偏差分别为0.09%、0.03%和0.04%。     

Liquid-liquid equilibrium for the quaternary system of o-xylene(1)+water(2) +propionic acid(3)+1-butanol(4) at 298.15 K and atmospheric pressure

The liquid-liquid equilibrium for the quaternary system of o-xylene(1)+water(2)+propionic acid(3)+1-butanol(4) was measured at 298.15 K and atmospheric pressure. Binodal curves, tie-lines, a distribution curve, and a selectivity curve for the quaternary system have been determined in order to investigate the effect of binary solvents, oxylene and 1-butanol, on extracting propionic acid from aqueous solution. In addition, these experimental tie line data were also compared with the values predicted by the UNIFAC model. In this study, the UNIFAC model was capable of predicting the compositions of this quaternary system within an average RMSD of 1.13 mol%. This paper was prepared at the 2004 Korea/Japan/Taiwan Chemical Engineering Conference held at Busan, Korea between November 3 and 4, 2004.     

固体酸S_2O_8~(2-)/Fe_2O_3-SiO_2催化合成乙酸丁酯的研究

本文研究了以S2 O82 -/Fe2 O3 -SiO2 固体酸为催化剂 ,以乙酸、丁醇为原料合成乙酸丁酯 ,考察了影响反应的因素 ,结果表明最佳工艺条件是 :固体酸催化剂前驱体经微波陈化处理 ,醇酸摩尔比为1.2∶1,催化剂用量为 0 .8g(乙酸用量为 0 .2mol的情况下 ) ,带水剂为 10mL ,反应时间为 3.0h ,酯化可达到97.7% ,可重复利用 6次以上     

Measurement and correlation of the isobaric vapor-liquid equilibrium for mixtures of alcohol+ketone systems at atmospheric pressure

Vapor-liquid equilibrium (VLE) for binary mixtures composed of ethanol+methyl isobutyl ketone, 1-butanol+ methyl ethyl ketone, and 1-butanol+methyl propyl ketone systems was measured using a circulation type equilibrium apparatus at atmospheric pressure. The measured data and literature data for alcohol and ketone systems have been correlated by the UNIversal Quasi-Chemical (UNIQUAC) model with two binary interaction parameters and the non-random lattice fluid equation of state with hydrogen bonding equation of state (NLF-HB EoS) using a single binary interaction parameter. For the NLF-HB EoS calculations, the numbers of proton acceptor for ketones were adjusted between 0 and 1. The calculation results with the NLF-HB EoS are better than those with the UNIQUAC model.     

低温精馏过程模拟及其分离特性分析 (Ⅰ)氢溶液状态方程及热力学性质计算

将Soave改进的BWR方程(1999年)应用于饱和氢流体,通过实验数据对方程的参数进行了选择和优化.此方程可用于饱和氢溶液气液两相p-V-T关系、热力学性质以及气液平衡关系的预测.对于H₂、D₂、T₂饱和流体,气相密度的平均相对误差分别为0.19905%、0.28173%、0.001295%,最大偏差分别为-0.99511%、4.6664%、-0.0040385%;液相密度的平均相对误差分别为0.5504%、0.33704%、0.04703%,最大偏差分别为3.2950%、-2.2629%、0.12126%,其准确性良好.可作为低温精馏分离氢同位素的一个严格的热力学模型.     

Measurement and modeling of vapor-liquid equilibrium for ternary system water + 2-propanol + 1-butyl-3-methylimidazoliumchloride简

Vapor-liquid equilibrium （VLE） data for water ＋ 2-propanol ＋ 1-butyl-3-methylimidazolium chloride （[bmim]Cl） were measured. Six sets of complete T, x, y data are reported, in which the 2-propanol mole fraction on IL-free basis is fixed separately at 0.1, 0.2, 0.4, 0.6, 0.8, and approximate 0.98, while the IL mass fraction is varied from 0.1 to 0.8, in an interval of 0.1. The non-random-two-liquid （NRTL） and electrolyte non-random-two-liquid （eNRTL） equations are used to correlate the experimental data with satisfactory results. The ternary VLE behavior is also modeled with the parameters obtained by correlating two data sets, in which the mole fraction of 2-propanol on IL-free basis is approximately 0.1 and 0.98. In this way, the six sets of data are reproduced satisfactorily. With the eNRTL model, the root-mean-square deviation for temperature is 0.82 K and that for vapor-phase mole fraction is 0.0078. The influences of IL on activity coefficients and relative volatility of the volatile components are also graphically illustrated.     

Study of Microemulsion Composition Effect over Phosphorescence Emission of a Polycyclic Aromatic Compound

A detailed characterization of the microemulsion composition is necessary to make the phosphorimetry suitable as powerful analytical methodology. Four microemulsion systems (hexane/ n -butanol/SDS/water, hexane/ n -pentanol/SDS/water, hexane/3-pentanol/SDS/water, and hexane/ n -hexanol/SDS/water) were studied, establishing the oil/water (O/W) microemulsion composition with best phosphorimetric characteristics (maximum phosphorescence intensity and minimum stabilization time). The different experimental variables that affect the phosphorimetric emission of the model compound selected named fluoranthene (i.e. concentrations of micellar agent, heavy atom, and oxygen scavenger) were carefully optimized and an analytical method for this analyte was proposed. The best results (maximum sensitivity and rapidity) were obtained using the hexane/ n -pentanol/SDS/water system with a 0.03% v/v of hexane and 0.05% v/v of n -pentanol, 0.92% v/v of SDS (0.5 M). Under these conditions, it is possible to observe an instantaneous phosphorescent signal of fluoranthene and develop a method with a detection limit of 2.2 ng mL m 1 and a relative standard deviation of 1.53% at a concentration level of 25 ng mL m 1.     

生物酶法合成(S)-2-氨基-1-丁醇的研究

以粪产碱杆菌来源的青霉素G酰化酶为催化剂,酶法拆分苯乙酰消旋底物转化生成(S)-2-氨基-1-丁醇。通过对催化过程中加酶量、底物浓度、反应温度、pH进行优化,确定最适酶催化条件是pH 9.0,40℃,底物浓度100 mmol/L,酶量2 U/mL,反应体积80 mL。在最适反应条件下,当消旋底物转化率达40%时终止反应可获得较高的产物光学纯度(ee>99%)。     

Orientation effect on sign and magnitude of excess thermodynamic functions of non electrolyte solutions at different temperatures (303.15 K, 308.15 K,and 313.15K)

Experimental values of the density and viscosity have been measured for binary mixtures of N-ethylaniline with isomeric butanols (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol) at 303.15, 308.15 and 313.15 K over the entire mole fraction range. These data, the excess molar volumes, and deviation viscosity for the binary systems at the above-mentioned temperatures were calculated and fitted to Redlich-Kister equation to determine the fitting parameters and the root-mean-square deviations. The excess molar volumes, deviation viscosity and excess Gibbs energy of activation of viscous flow have been analyzed in terms of acid-base interactions, hydrogen bond, and dipole-dipole interaction between unlike molecules. The results obtained for dynamic viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, Katti-Chaudhri, and Hind et al. equations.     

丁醇和高级烷烃气液相平衡的分子模拟

用Gibbs系综的Monte Carlo法模拟了正丁醇。正己烷和正丁醇-正庚烷体系的气液相平衡。在恒定压力0.496 6 MPa、0.294 0 MPa和0.1 MPa下,分别采用恒温恒压的Gibbs系综(NPT-Gibbs)模拟了不同温度下的气液相平衡。计算结果表明,模拟的数据比较准确,在一定温度范围内与实验结果吻合。     

水/二甲基乙酰胺/聚砜体系双结点线的神经网络预测

基于实验数据,采用人工神经网络对水/二甲基乙酰胺/聚砜体系的双结点线进行了预测. 设计并验证了具有两个输入神经元(体系温度和聚砜的质量分数)和两个输出神经元(水和二甲基乙酰胺的质量分数)的BP(Back Propagation)网络, 选取50组训练样本和39组检验样本分别对网络进行了训练与检验. 结果表明,对水与二甲基乙酰胺质量分数的预测平均相对误差分别为1.86%和0.10%. 采用该网络能较好地预测常压下、20~60℃温度范围内水/二甲基乙酰胺/聚砜体系的双结点线.     

常压下乙醇-水-醋酸钾系统汽液平衡数据的测定与关联

采用Ellis汽液两相双循环平衡蒸馏仪测定了常压下乙醇(1)-水(2)和乙醇(1)-水(2)-醋酸钾(3)物系的汽液平衡数据,结果表明：醋酸钾对乙醇(1)-水(2)系统具有盐析效应,乙醇对水的相对挥发度α₁₂上升。系统中10%(质量)的醋酸钾已经消除了乙醇-水间的共沸点,可作为加盐萃取精馏的分离剂。采用已授权的Aspen Plus软件自带的eNRTL、Wilson和UNIQUAC模型,以及eNRTL模型分别对乙醇(1)-水(2)、乙醇(1)-水(2)-10%(质量)醋酸钾(3)系统实验数据进行了关联,计算结果表明：乙醇(1)-水(2)系统中,平衡温度的平均绝对偏差（AAD）为0.72℃(eNRTL)、0.78℃(Wilson)和0.71℃(UNIQUAC),气相组成计算值的平均绝对偏差为0.0083(eNRTL)、0.0077(Wilson)和0.0101(UNIQUAC)。而在乙醇(1)-水(2)-10%(质量)醋酸钾(3)系统中平衡温度和气相组成平均绝对偏差分别为0.25℃和0.0168(eNRTL)。     

Lipase-Mediated Synthesis of Fatty Acid Esters Using a Blending Alcohol Consisting of Methanol and 1-Butanol

Lipase-mediated transesterification of soybean oil with a blending alcohol consisting of methanol and 1-butanol for synthesis of fatty acid esters was carried out. Lipase from Thermomyces lanuginosa (Lipozyme TL IM) was used as a biocatalyst. The lipase was purchased from Novozymes (Seoul, Republic of Korea). The effects of the molar proportions of methanol and 1-butanol in the blending alcohol, reaction temperature, enzyme loading and water content were investigated, for reaction optimization. The relative consuming rates of methanol and 1-butanol during the reaction were also explored. Among seven different ratios of alcohol blends employed in this study, that containing 80 mol% methanol gave the highest yield of fatty acid esters. Optimum reaction temperature, enzyme loading, and water content were 30 °C, 15% (based on the substrate weight), and 0.3% (based on the substrate weight), respectively. Water influenced significantly the reaction rate and yield. On the transesterification, the degree of reaction of methanol was higher than that of 1-butanol and the presence of 1-butanol contributed to increase of the reaction rate as well as yield. The maximum yield of ca. 98 wt% was achieved under the optimized condition.