BUBBLE TEMPERATURES OF THE BINARY MIXTURES OF 1,2-DIMETHYLBENZENE WITH 2-PROPANOL, 1-BUTANOL, 2-BUTANOL, 2-METHYLPROPAN-1-OL AND 2-METHYLPROPAN-2-OL AT 95 kPa

Bubble temperatures at 95?kPa over the entire composition range are measured for the five binary systems formed by 1,2-dimethylbenzene with 2-propanol, 1-butanol, 2-butanol, 2- methylpropan-1-ol, and 2-methylpropan- 2-ol. A Swietoslawski - type ebulliometer was used for the measurements. The composition versus temperature measurements are well represented by the Wilson model.     

BUBBLE TEMPERATURE MEASUREMENTS ON THE BINARY MIXTURES OF 1,4-DIMETHYLBENZENE WITH ISO-, SEC-, AND TERT- BUTANOLS AT 95 kPa

Bubble temperatures at 95 kPa over the entire composition range were measured for the three binary systems formed by 1,4-dimethylbenzene with iso-, sec-, and tert- butanols. A Swietoslawski-type ebulliometer was used for the measurements. The composition versus temperature measurements are well represented by the Wilson model.     

BUBBLE TEMPERATURE MEASUREMENTS ON THE BINARY MIXTURES OF 1,4-DIMETHYLBENZENE WITH ISO -, SEC -, AND TERT - BUTANOLS AT 95 kPa

Bubble temperatures at 95 kPa over the entire composition range were measured for the three binary systems formed by 1,4-dimethylbenzene with iso-, sec-, and tert- butanols. A Swietoslawski-type ebulliometer was used for the measurements. The composition versus temperature measurements are well represented by the Wilson model.     

BOILING POINT TEMPERATURES OF THE BINARY MIXTURES OF 1,3-DIMETHYLBENZENE WITH METHANOL, 1-PROPANOL, OR 2-PROPANOLAT 95 kPA

Boiling point temperatures at 95 kPa over the entire composition range are measured for the three binary systems formed by 1,3-dimethylbenzene with methanol, 1-propanol, and 2-propanol. A Swietoslawski-type ebulliometer was used for the measurements. The composition versus temperature measurements are well represented by the Wilson model.     

EXCESS GIBBS ENERGY FOR THE BINARY MIXTURES OF NITROBENZENE WITH SOME HYDROCARBONS AT 94.95KPA

Bubble point temperatures at 94.95 kPa, over the entire composition range, are measured for the binary mixtures of nitrobenzene with: cyclohexane, n-hexane, n-heptane, n-decane, and o-, m-, and p-xylenes, using a Swietoslawski-type ebulliometer. Liquid phase composition versus bubble point temperature measurements are well represented by the Wilson model. Computed values of the excess Gibbs energy are presented and discussed.     

1—甲氧基—2—丙醇的合成研究

阐述了利用环氧丙烷和甲醇在催化剂HM-9512存在下,通过选择性开环加成制备1-甲氧基-2-丙醇的工艺过程。讨论了几个主要反应因素对产物选择性和收率的影响,确定了适宜的工艺条件和产品的检测方法。     

环己烷、正丁醇、甲苯有关二元体系加压相平衡

以环已烷、正丁醇、甲苯为代表,进一步研究了烷烃、芳烃和低级醇在加压下的相平衡规律。测定了有关3个二元体系在101.3、304.0、506.6、709.3、911.9kPa下汽液平衡数据,对实测数据进行了统一关联,计算结果与实测值符合良好。环己烷-正丁醇、正丁醇-甲苯体系在所测压力下均形成最低共沸点。     

THERMODYNAMIC PROPERTIES OF BINARY LIQUID MIXTURES OF ETHANE AND ETHYLENE WITH METHANE AND THE RARE GASES

Two series of binary liquid mixtures containing either ethylene or ethane have been investigated, at one or more temperatures (usually at the triple-point temperature of the component with the higher melting-point). In the ethylene series liquid-vapour equilibrium and liquid density studies were carried out for mixtures with methane, krypton and xenon; the heats of mixing were also measured for the ethylene + krypton mixtures. In the ethane series, which comprised mixtures with methane, argon, krypton and xenon, all three properties were measured except for the ethane + methane and ethane + argon systems where the enthalpies of mixing were already known. The ethylene + ethane system was also investigated at 161.39 K.

The results have been used to estimate the thermodynamic excess functions G^E , V^E and H^E . The G^E values decrease, within each series, as one moves from the lighter to the heavier rare gas, the values being lower in the ethane series. For the ethane + xenon mixtures both G^E and H^E are negative, showing a weak attraction between the two molecules. The V^E values for the mixtures of hydrocarbons suggest the probable formation of interlocking structures between the two components.

The values of the thermodynamic excess functions have been interpreted in the light of the model of Frisch-Longuet Higgins-Widom for the liquid state.     

反应精馏合成2-羟丙基甲醚的研究

以甲醇和环氧丙烷为反应物,采用均相连续反应精馏法合成了２－羟丙基甲醚。对三乙胺、氢氧化钠、氢氧化钾、碳酸钠和碳酸钾五种催化剂的催化活性和选择性进行了研究。考察了以三乙胺为催化剂时进料摩尔比和环氧丙烷进料速率对环氧丙烷转化率、２－羟丙基甲醚选择性及收率的影响,并对反应精馏塔的温度分布进行了讨论     

A SIMPLE CALCULATION OF THE PRESSURE AND LIQUID MOLE FRACTION AT THE VLE OF ETHANE/LIGHT HYDROCARBON BINARY MIXTURES

An analytical expression for the calculation of the pressure and liquid mole fraction at the VLE of ethane/light hydrocarbon binary mixtures is proposed. The model is based on a simple analytical expression for the vapor pressure of pure non-polar fluids, which, for a given temperature, only requires as input the values of the Lennard-Jones molecular parameters and the acentric factor. A properly modified Lorentz-Berthelot mixing rule is used, the interaction parameters being given as simple functions of the temperature and composition with eight constants for each binary mixture. The model is shown to reproduce accurately and simply the pressure (for a given liquid mole fraction) or the liquid composition (for a given pressure) of six ethane + hydrocarbon systems at different temperatures.     

SYNERGISTIC EXTRACTION OF CADMIUM AND ZINC WITH 1-PHENYL-3-METHYL-4-BENZOYLPYRAZOL-5-OL AND n-DODBCYLAMINE MIXTURES,EMULSION FORMATION.

The synergistic extraction of zinc and cadmium (M^2*) from sulphate, nitrate and perchlorate media with mixtures of 1-phenyl-3-methyl-4-benzoylpyra2ol-5-ol (HL) and n-dodecylammoniura salts (DDAH^*,X^?) in toluene has been studied. In sulphate medium, the lipophilic ammonium pyrazololate (DDAK^*L^?) is the predominating ammonium species : the synergy observed can be considered as the addition of (DDAH^*,L^?) on HL₂ perchlorate and nitrate media, the amphiphilic ammonium salts {DDAH^*, CIO₄?) and (DDAH⁺N0₃ ^?) predominate, leading to the formation of an aqueous emulsion in equilibrium with a clear organic phase. Metal distribution curves show that the formation of the lipophilic synergistic species (DDAH⁺ML₂ ^?) results from a X^?/ML₃ ^? exchange in the interfacial region between the aqueous and the organic phase. The addition of n-octanol or 4-nonylphenol in the organic phase turns the emulsion into a micro-emulsion whereas the substitution of toluene by chloroform largely decreases the emulsion stability.     

CALCULATION OF THE BINARY INTERACTION AND NONRANDOMNESS PARAMETERS OF NRTL,NRTL1, AND NRTL2 MODELS USING GENETIC ALGORITHM FOR TERNARY IONIC LIQUID SYSTEMS

One of the most important applications of thermodynamics is the accurate prediction of fluid phase equilibria problems related to real chemical engineering processes. Various equations of state as well as activity coefficient models have been developed for such calculations with many interaction, size, and randomness parameters, which should be optimized based on powerful and effective computational methods. Leading to globally optimal values, genetic algorithm (GA) as a powerful and effective tool can be used for prediction of the interaction parameters of thermodynamic models in complex liquid-liquid equilibrium (LLE) systems. It requires only lower and upper bounds for the interaction parameters and the necessary initial guesses are produced automatically. In the present work, based on the GA method, a global optimization procedure is introduced for calculation of the binary interaction and nonrandomness parameters of NRTL, NRTL1, and NRTL2 activity coefficient models for 20 ternary aromatic extraction systems containing 16 different ionic liquids at various temperatures. The values of the parameters along with the root-mean-square deviations (rmsd) are reported. The results, in terms of rmsd for NRTL, NRTL1, and NRTL2 models, are very satisfactory, with global values of 0.0031, 0.0020, and 0.0053 for 187 tie-lines respectively. The obtained rmsd values for the NRTL model using the GA method are better than those reported in the literature. The rmsd results for the three studied models show that NRTL1 can handle the LLE calculations with more accuracy than the original NRTL and NRTL2 activity coefficient models.     

用鼓泡平衡釜测定高温汽液平衡数据及对总压测定的探讨

本文用改进了的鼓泡平衡釜测定了均三甲苯-偏三甲苯体系在411.4K、424.2K、437.0K三个温度下,以及甲苯-正丁醇体系在353.5K及373.2K二个温度下的汽液平衡数据,所得数据均通过热力学一致性检验,实验数据用Wilson方程进行了关联,两个二元体系的计算值与实验值的偏差|△Y|<0.005,△Ymax<0.01。文中还就鼓泡平衡釜总压确定问题进行了探讨。     

高温低热导率隔热材料的研究现状及进展

新型隔热材料的一个重要发展方向是具有高温低热导率的复合材料的研究和开发。重点对硅酸铝纤维、六钛酸钾晶须及气凝胶二氧化硅隔热材料的特点进行了综述,探讨了几种颇具前景的高效高温隔热材料。     

ALTERNATIVE GENERATION OF H2, CO AND H2, CO2 MIXTURES FROM STEAM-CARBON DIOXIDE REFORMING OF METHANE AND THE WATER GAS SHIFT WITH PERMEABLE (MEMBRANE) REACTORS

A new process is proposed which converts CO₂ and CH₄ containing gas streams to synthesis gas, a mixture of CO and H₂ via the catalytic reaction scheme of steam-carbon dioxide reforming of methane or the respective one of only carbon dioxide reforming of methane, in permeable (membrane) reactors. The membrane reformer (permreactor) can be made by reactive or inert materials such as metal alloys, microporous ceramics, glasses and composites which all are hydrogen permselective. The rejected CO reacts with steam and converted catalytically to CO₂ and H₂ via the water gas shift in a consecutive permreactor made by similar to the reformer materials and alternatively by high glass transition temperature polymers. Both permreactors can recover H₂ in permeate by using metal membranes, and H₂ rich mixtures by using ceramic, glass and composite type permselective membranes. H₂ and CO₂ can be recovered simultaneously in water gas shift step after steam condensation by using organic polymer membranes. Product yields are increased through permreactor equilibrium shift and reaction separation process integration.

CO and H₂ can be combined in first step to be used for chemical synthesis or as fuel in power generation cycles. Mixtures of CO₂ and H₂ in second step can be used for synthesis as well (e.g., alternative methanol synthesis) and as direct feed in molten carbonate fuel cells. Pure H₂ from the above processes can be used also for synthesis or as fuel in power systems and fuel cells. The overall process can be considered environmentally benign because it offers an in-situ abatement of the greenhouse CO₂ and CH₄ gases and related hydrocarbon-CO₂ feedstocks (e.g., coal, landfill, natural, flue gases), through chemical reactions, to the upgraded calorific value synthesis gas and H₂, H₂ mixture products.     

DEGRADATION OF AQUEOUS SOLUTIONS OF ALKANOLAMINE BLENDS AT HIGH TEMPERATURE, UNDER THE PRESENCE OF CO2 AND H2S

An experimental study on the degradation of aqueous solutions of alkanolamine blends, under the presence of carbon dioxide and hydrogen sulfide, was carried out. The studied alkanolamines were: diethanolamine (DEA), methyldiethanolamine (MDEA), and 2-amino-2-methyl-1-propanol (AMP). Degradation experiments were carried out at a temperature of 200°C. The mass fraction of DEA and MDEA in the studied aqueous solutions was 10% and 35%, respectively. AMP was incorporated into the MDEA-DEA aqueous solutions, with concentrations of (0-8) mass fraction. Partially degraded alkanolamine aqueous solutions were analyzed, after about 90 hours, by gas chromatography.

It was found that in all the studied alkanolamine aqueous solutions the MDEA degrades more slowly than DEA under the same experimental conditions. Degradation of both alkanolamines was found to be almost independent of the AMP concentration. AMP exhibits an intermediate stability; it is more resistant to degradation than DEA but less than MDEA. In addition, thermal degradation of DEA and MDEA is minimal up to 200°C.     

ALTERNATIVE GENERATION OF H2, CO AND H2, CO2 MIXTURES FROM STEAM-CARBON DIOXIDE REFORMING OF METHANE AND THE WATER GAS SHIFT WITH PERMEABLE (MEMBRANE) REACTORS

A new process is proposed which converts CO₂ and CH₄ containing gas streams to synthesis gas, a mixture of CO and H₂ via the catalytic reaction scheme of steam-carbon dioxide reforming of methane or the respective one of only carbon dioxide reforming of methane, in permeable (membrane) reactors. The membrane reformer (permreactor) can be made by reactive or inert materials such as metal alloys, microporous ceramics, glasses and composites which all are hydrogen permselective. The rejected CO reacts with steam and converted catalytically to CO₂ and H₂ via the water gas shift in a consecutive permreactor made by similar to the reformer materials and alternatively by high glass transition temperature polymers. Both permreactors can recover H₂ in permeate by using metal membranes, and H₂ rich mixtures by using ceramic, glass and composite type permselective membranes. H₂ and CO₂ can be recovered simultaneously in water gas shift step after steam condensation by using organic polymer membranes. Product yields are increased through permreactor equilibrium shift and reaction separation process integration.

CO and H₂ can be combined in first step to be used for chemical synthesis or as fuel in power generation cycles. Mixtures of CO₂ and H₂ in second step can be used for synthesis as well (e.g., alternative methanol synthesis) and as direct feed in molten carbonate fuel cells. Pure H₂ from the above processes can be used also for synthesis or as fuel in power systems and fuel cells. The overall process can be considered environmentally benign because it offers an in-situ abatement of the greenhouse CO₂ and CH₄ gases and related hydrocarbon-CO₂ feedstocks (e.g., coal, landfill, natural, flue gases), through chemical reactions, to the upgraded calorific value synthesis gas and H₂, H₂ mixture products.     

DENSITIES AND DERIVED THERMODYNAMIC PROPERTIES OF THE BINARY SYSTEMS OF BENZENE WITH BUTYL METHACRYLATE, ALLYL METHACRYLATE, METHACRYLIC ACID, AND VINYL ACETATE AT 298.15K

Densities of the binary systems of benzene with butyl methacrylate, allyl methacrylate, methacrylic acid, and vinyl acetate have been measured as a function of the composition, at 298.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densimeter. The calculated excess molar volumes were correlated with the Redlich-Kister equation and with a series of Legendre polynomials. The excess molar volumes are positive for the four binaries studied.