常压下二乙二醇单乙醚和水二元体系不同温度下的密度、黏度及过量性质

Densities and viscosities were measured as a function of composition for binary liquid mixture of diethylene glycol monoethyl ether [CH3CH2O(CH2)2O(CH2)2OH] + water from 293.15 to 333.15 K at atmospheric pressure, with a capillary pycnometer and Ubbelohde capillary viscometer respectively. From the experimental data, the excess molar volume VE, viscosity deviation η, and the excess energy of activation for viscous flow G*E were calculated. These data were correlated by the Redlich-Kister type equa-tions to obtain the coefficients and standard deviations. The results showed a strong molecular interaction between diethylene glycol monoethyl ether and water.     

Determination and correlation solubility of m-phenylenediamine in (methanol,ethanol, acetonitrile and water) and their binary solvents from 278.15 K to 313.15 K

In this study, the solubility of m-phenylenediamine in four pure solvents(methanol, ethanol, acetonitrile and water) and three binary solvent(methanol + water),(ethanol + water) and(acetonitrile + water) systems were determined in the temperature ranging from 278.15 K to 313.15 K by using the gravimetric method under atmospheric pressure. In the temperature range of 278.15 K to 313.15 K, the mole fraction solubility values of m-phenylenediamine in water, methanol, ethanol, and acetonitrile are 0.0093–0.1533, 0.1668–0.5589,0.1072–0.5356, and 0.1717–0.6438, respectively. At constant temperature and solvent composition, the mole fraction solubility of o-phenylenediamine in four pure solvents was increased as the following order:water b ethanol b methanol b acetonitrile; and in the three binary solvent mixtures could be ranked as follows:(ethanol + water) b(methanol + water) b(acetonitrile + water). The relationship between the experimental temperature and the solubility of m-phenylenediamine was revealed as follows: the solubility of mphenylenediamine in pure and binary solvents could be increased with the increase of temperature. The experimental values were correlated with the Jouyban–Acree model, van't Hoff–Jouyban–Acree model, modified Apelblat–Jouyban–Acree model, Sun model and Ma model. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated based on the experimental solubility data. In the binary solvent mixtures, the dissolution of m-phenylenediamine could be an endothermic process. The solubility data,correlation equations and thermodynamic property obtained from this study would be invoked as basic data and models regarding the purification and crystallization process of m-phenylenediamine.     

1,2-丙二醇水溶液在不同温度下的超额摩尔体积黏度和热容

Experimental densities, viscosities and heat capacities at different temperatures were presented over the entire mole fraction range for the binary mixture of 1,2-propanediol and water. Density values were used in the determination of excess molar volumes, VE. At the same time, the excess viscosity was investigated. The values of VE and E were fitted to the Redlich-Kister equation. Good agreement was observed. The excess volumes are negative over the entire range of composition. They show an U-shaped-concentration dependence and decrease in absolute values with increase of temperature. Values of E are negative over the entire range of the composition, and has a trend very similar to that of VE . The analysis shows that at any temperature the specific heat of mixture is a linear function of the composition as x1 > 20%. All the extended lines intersect at one point. An empirical equation is obtained to calculate the specific heat to mixture at any composition and temperature in the experimental range.     

共沸混合物（R290/CO2）跨临界动力循环性能分析（英文）

Low critical temperature limits the application of CO2 trans-critical power cycle. The binary mixture of R290/CO2 has higher critical temperature. Using mixture fluid may solve the problem that subcritical CO2 is hardly con-densed by conventional cooling water. In this article, theoretical analysis is executed to study the performance of the zeotropic mixture for trans-critical power cycle using low-grade liquid heat source with temperature of 200 °C. The results indicated that the problem that CO2 can't be condensed in power cycle by conventional cooling water can be solved by mixing R290 to CO2. Variation trend of outlet temperature of thermal oil in super-critical heater with heating pressure is determined by the composition of the mixture fluid. Gliding temperature causes the maximum outlet temperature of cooling water with the increase of mass fraction of R290. There are the maximum values for cycle thermal efficiency and net power output with the increase of supercritical heating pressure.     

Solubilities of CO2 in some glycol ethers under high pressure by experimental determination and correlation☆

The binary vapor–liquid equilibrium data of CO_2 in diethylene glycol(monomethyl,monoethyl,monobutyl,dimethyl,diethyl,dibutyl)ether were determined from 288.15 to 318.15 K at pressure up to 6 MPa based on the constant-volume method.It was found by contrast that the ether group in solvents can promote the CO_2 absorption,but the hydroxyl group will inhibit the CO_2 absorption.Furthermore,the solubilities of CO_2 showed an upward trend with the increasing molecular lengths of absorbents.The experimental data were also correlated with a modified Patel–Teja equation of state(PT EOS)combined with the traditional van der Waals one-fluid mixing rules and the results showed a satisfactory agreement between the model and the experimental data.     

Solubility of the silver nitrate in supercritical carbon dioxide with ethanol and ethylene glycol as double cosolvents: Experimental determination and correlation

Solubility of the silver nitrate in the supercritical carbon dioxide containing ethanol and ethylene glycol as double cosolvents was measured under certain pressure and temperature range(10–25 MPa, 323.15–333.15 K). The impact of the pressure and temperature on the solubility was also investigated. Based on the experiment data,a correlation model concerning solid's solubility in supercritical fluids was established by combining the solubility parameter with the thermodynamic equation when a binary interaction parameter and a mixed solvent solubility parameter were defined. Experiments show the solubility of AgNO_3 increases with the pressure at a certain temperature. However, the influence of temperature is related to a pressure defined as the turnover pressure(12.3 MPa). When the pressure is higher(or lower) than this turnover pressure, silver nitrate's solubility shows increasing(or decreasing) trend as the temperature rises. Satisfactory accuracy of our presented model was revealed by comparing experimental data with calculated results.     

Measurement and correlation of solubility of meropenem trihydrate in binary (water + acetone/tetrahydrofuran) solvent mixtures

The solubility of meropenem trihydrate in water + acetone mixtures and water + tetrahydrofuran mixtures were determined from T =(278.15 to 303.15) K by static method under atmospheric pressure.Effects of solvent composition and temperature on solubility of meropenem trihydrate were discussed.To extend the applicability of the solubility data,experimental solubility data in two kinds of binary solvent mixtures were correlated by the Apelblat equation and NIBS/Redlich-Kister model.It was found that the two models could satisfactorily correlate the experimental data and the Apelblat equation could give better correlation results.     

采用增大凝结液滴方法的锥芯超音速旋流分离装置性能研究

To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation centers. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of %-0 in most cases.     

近临界水中水解鱼蛋白制备氨基酸

The hydrolysis technology and reaction kinetics for amino acids production from fish proteins in subcritical water reactor without catalysts were investigated in a reactor with volume of 400 ml under the conditions of reaction temperature from 180-320℃, pressure from 5-26 MPa, and time from 5-60 rain. The quality and quantity of amino acids in hydrolysate were determined by bioLiquid chromatography, and 17 kinds of amino acids were obtained. For the important 8 amino acids, the experiments were conducted to examine the effects of reaction temperature, pressure and time on amino acids yield. The optimum conditions for high yield are obtained from the experimental results. It is found that the nitrogen and carbon dioxide atmosphere should be used for leucine, isoleucine and histidine production while the air atmosphere might be used for other amino acids. The reaction time of 30 rain and the experimental temperature of 220℃, 240℃ and 260℃ were adopted for reaction kinetic research. The total yield of amino acids versus reaction time have been examined experimentally. According to these experimental data and under the condition of water excess, the macroscopic reaction kinetic equation of fish proteins hydrolysis was obtained with the hydrolysis reaction order of 1.615 and the rate constants being 0.0017, 0.0045 and 0.0097 at 220℃, 240℃ and 260℃ respectively. The activation energy is 145.1 kJ·mol^- 1.     

应用于低温加热的肉豆蔻酸和硬脂酸共熔混合物的储热特性

Stearic acid （67.83℃） and myristic acid （52.32℃） have high melting temperatures that can limit their use as phase change material （PCM） in low temperature solar heating applications such as solar space and greenhouse heating in regard to climatic requirements. However, their melting temperatures can be adjusted to a suitable value by preparing a eutectic mixture of the myristic acid （MA） and the stearic acid （SA）. In the present study, the thermal analysis based on differential scanning calorimetry （DSC） technique shows that the mixture of myristic acid （MA） and stearic acid （SA） in the respective composition （by mass） of 64% and 36% forms a eutectic mixture having melting temperature of 44.13℃ and the latent heat of fusion of 182.4J.g^-1. The thermal energy storage characteristics of the MA-SA eutectic mixture filled in the annulus of two concentric pipes were also experimentally established. The heat recovery rate and heat charging/discharging fractions were determined with respect to the change in the mass flow rate and the inlet temperature of heat transfer fluid. Based on the results obtained by DSC analysis and by the heat charging/discharging processes of the PCM, it can be concluded that the MA-SA eutectic mixture is a potential material for low temperature thermal energy storage applications in terms of its thermo-physical and thermal characteristics.     

管式反应器液相循环反应制备二甘醇乙烯基醚

以乙炔和二甘醇为原料,二甘醇钾为催化剂,采用管式反应器液相循环反应制备二甘醇乙烯基醚。研究了催化剂用量、反应温度、反应压力和停留时间等因素对乙炔转化率的影响,得到较为适宜的反应条件为：催化剂二甘醇钾用量为二甘醇质量的4%、反应温度175℃、反应压力6MPa、停留时间175s。在该条件下进行了液相连续循环反应,反应达到稳态时,二甘醇的转化率为76.03%,二甘醇单乙烯基醚收率为59.03%,二甘醇双乙烯基醚的收率为15.10%,合计二甘醇乙烯基醚总收率为74.13%。单位反应体积二甘醇乙烯基醚的产率为143.2g/（h·mL）。二甘醇与乙炔反应符合一级反应动力学方程,反应的指前因子k₀=1.20×10⁸s^–1,反应的活化能E=86.86kJ/mol。管式反应器中无气相乙炔,克服了高温高压下气相乙炔易燃易爆的危险。     

烯丙基醚葡萄糖苷的制备和表征

以对甲苯磺酸为催化剂,葡萄糖和二乙二醇单烯丙基醚反应制备了二乙二醇单烯丙基醚葡萄糖苷。考察了反应物配比、反应时间、反应温度和催化剂用量对糖苷聚合度的影响。结果表明:n(葡萄糖)∶n(二乙二醇单烯丙基醚)=1∶4,催化剂用量为葡萄糖质量的3.2%,反应温度110℃,反应时间5h的条件下所得产品平均聚合度可达到1.06。     

Soybean oil microemulsions with oleic acid/glycols as cosurfactants

The preparation of biocompatible microemulsions of soybean oil in systems made of anionic surfactant, oleic acid, water, and several glycols was considered. The selected glycols were ether derivatives (methyl, ethyl, dimethyl, and diethyl ether) of ethylene glycol and diethylene glycol. The study was performed using pseudoternary phase diagrams in which the three apexes were occupied by soybean oil, a combination of surfactant/oleic acid, and a combination of water/glycol, respectively. The widest regions of microemulsions were obtained for systems containing methyl ether and especially ethyl ether of both ethylene glycol and diethylene glycol. The two latter compounds allowed the preparation of oil-in-water, bicontinuous, and water-in-oil microemulsions with final surfactant contents of 3–4%.     

有机硅-苯丙乳液最低成膜温度的研究

采用半连续法制备了稳定的有机硅-苯丙乳液，研究了软硬单体配比和有机硅单体含量对共聚物玻璃化转变温度(Tg)和乳液最低成膜温度(MFT)的影响：并选用3种成膜助剂(TXL、DPD和二乙二醇二乙醚)分别考察了成膜助剂的种类和用量对乳液产品MFT的影响。结果表明，共聚物T和乳液的MFT呈较好的线性关系，该乳液体系MFT/Tg约为0．97；乳液产品的MFT随成膜助剂用量的增加而大幅降低，其中二乙二醇二乙醚的效果最好。     

Hydrophobic hydration of cationic mixed micelles by alkoxyethanols in aqueous media

The conductances of hexadecylpyridinium chloride (HPyCl) + tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HPyCl (α_HPyCl) were measured in aqueous binary mixtures of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether containing 10 to 30 wt% additive in their respective binary mixtures at 30°C. Each conductivity curve showed a single break over the whole mole fraction range of HPyCl + TTAB mixtures. From the break in the conductivity curve, various micellar parameters were calculated and the results were discussed on the basis of alkoxyethanol's hydrophobic hydration of the mixed micelle. The micellar parameters of HPyCl, TTAB, and of their mixtures showed a strong dependence both on the amount and on the number of repeating units of ethylene and diethylene glycol derivatives. The hydrophobic hydration was considerably higher in the case of diethylene glycol derivatives owing to the presence of an extra ether oxygen. An evaluation of the non-ideality in the HPyCl + TTAB mixtures in the presence of additives revealed that alkoxyethanols reduce the unlike surfactant monomer interactions in order to form the mixed micelles in comparison to those in pure water. It has also been observed that such interactions systematically decrease with an increase in the number of repeating units from monomethyl ether to monobutyl ether, both in the case of ethylene and diethylene glycol derivatives.     

Alkaline depolymerization of poly(trimethylene terephthalate)

The purpose of this study was to investigate the effects of reaction media, composition, and temperature on the rate of the alkaline depolymerization of poly(trimethylene terephthalate) (PTT). The alkaline depolymerization of PTT was carried out at 160–190°C in ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether (DEGMEE), and a mixture of these solvents. During the reaction, PTT was quantitatively converted to disodium terephthalate and 1,3-propanediol. The alkaline depolymerization reaction rate constants were calculated based on the concentration of sodium carboxylate, which was equivalent to the molar amount of sodium hydroxide. The depolymerization rate of PTT was increased by increasing the reaction temperature and by adding ethereal solvents. Moreover, the depolymerization rate was significantly accelerated in the order of EG < DEG < TEG < EGMBE < DEGMEE. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 99–107, 2001     

一缩二乙醇二缩水甘油醚双丙烯酸酯的合成

以一缩二乙二醇二缩水甘油醚(DGDE)和丙烯酸为原料,N,N-二甲基苄胺为催化剂,对羟基苯甲醚为阻聚剂,制得了一缩二乙二醇二缩水甘油醚双丙烯酸酯(ADGDE)。讨论了催化剂用量、反应温度等因素对反应的影响,并用FT-IR和Photo-DSC对ADGDE的化学结构及光固化行为进行了表征。结果表明,反应温度为100℃、催化剂用量为1 0%时催化效果和反应速率较理想,用对羟基苯甲醚作阻聚剂得到的ADGDE颜色较浅;ADGDE的光聚合速率随光引发剂的用量增加而提高。     

缩醛交换反应制备双二乙二醇丁醚缩甲醛

报道了一种以二乙二醇丁醚（DEGB）和二乙氧基甲烷（DEM）为原料,通过磷钨酸催化下的缩醛交换反应,合成双二乙二醇丁醚缩甲醛（BDEGBF）的新方法;与甲醛相比,二乙氧基甲烷可作为一种绿色的反应试剂应用于缩醛交换反应。考察了催化剂种类、催化剂用量、原料配比、反应温度、反应时间等因素对缩醛交换反应的影响。结果表明：当磷钨酸催化剂用量为二乙二醇丁醚质量的1.0%,原料配比n（DEM）：n（DEGB）=3：1,反应温度为80℃,反应时间为90min时,DEGB的转化率达到最高为84.9%。磷钨酸催化剂回收方便,可重复使用6次。通过FTIR和¹H NMR对产物结构进行表征,并提出了缩醛交换反应可能的反应机理。本缩醛制备方法具有多个优点,例如反应条件温和、环境友好、操作简便,还具有一定的醇醚类底物普适性。     

CO《,2》在碳酸二甲酯混合溶剂中的溶解度

为改善碳酸二甲酯(DMC),对CO<,2>气体的吸收性能,降低溶剂成本,在DMC中添加一定量的氨水、助溶剂形成拟均相混合CO<,2>吸收剂.用恒定容积法考察了不同条件下(助溶剂的类型、二乙二醇乙醚的比例、氨水的质量分数、氨水的比例和温度)混合溶剂(DMC+质量分数10%氨水+二乙二醇乙醚)的CO<,2>吸收性能.结果表...