A three-phase nonequilibrium model for catalytic distillation

Nonequilibrium model for steady state simulation of catalytic distillation is presented. Mathematical model takes into account both mass and heat transfers across the gas liquid interface and through the liquid-solid (catalyst) interface. Equations describing the mentioned phenomena are based on the effective diffusivity approach. The resulting system of nonlinear algebraic equations was implemented in the FORTRAN programming language and solved by the BUNLSI (Ferraris & Tronconi, 1986) solver. The described model was verified using the experimental data obtained from a continuous distillation column equipped with catalytic packing. As an experimental model system, synthesis of propyl propionate from propan-1-ol and propionic acid was chosen. Comparison of experimental and simulation data is presented, and appropriateness of the developed model for other types of catalytic distillation processes is discussed. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 26–30 May 2008.     

水蒸汽蒸馏条件下鱼腥草中癸酰乙醛的高效提取及质谱定性

根据质谱学规律,剖析了在电子轰击下中药材鱼腥草中最关键的抗菌成分鱼腥草素(癸酰乙醛)的离子形成机理:癸酰乙醛的分子中存在两个-C=O,处于端位上的-C=O活性远大于-CH3,易失去H2O(M+18)、CO(M+ 28)等基团,产生较强的m/z180、170等离子碎片,此外,还易失去H2O+H2O(M+ -36)、H2O+CO(M+-46)、CO+CO(M+-56)等基团,产生m/z162、152、142等离子碎片,这同实验中得到的癸酰乙醛质谱图完全吻合,纠正了文献中对癸酰乙醛的错误定性.在此基础上采用常规、Ar气保护和减压三种水蒸汽蒸馏方式提取鱼腥草挥发油,发现在惰性气氛或较低温度下有利于癸酰乙醛的提取,与常规水蒸汽蒸馏条件相比,Ar气保护下癸酰乙醛的含量从0.03％提高至0.53％,而减压条件下癸酰乙醛的溶出效率进一步提高至3.37％.研究表明常规水蒸汽蒸馏条件下癸酰乙醛易氧化分解是得到较少癸酰乙醛的根本原因.     

A novel single particle study of steam gasification kinetics of a coal-derived char at high temperatures and pressures

A novel single particle experiment was developed to allow for detailed char gasification measurements in pure steam at temperatures from 1000 °C to 1400  °C and pressures from 1  bar to 15  bar. A coal-derived activated carbon was thoroughly characterized with respect to its composition, physical structure, and reactivity revealing properties consistent with chars reported in the literature. The single particle approach allowed for the boundary and initial conditions to be well known and for the mass of the particle to be accurately measured before and after testing to provide high-quality conversion data. The resulting conversion data were analyzed using the random pore model and the shrinking core model, of which the random pore model provided the best fit. Apparent activation energies were calculated using the random pore model which provided values ranging from 57.1 kJ/mol to 129 kJ/mol which are nominally half of the magnitude of the values reported in the literature under kinetically controlled conditions, thus demonstrating that regime II conditions were present. Additionally, the activation energies decreased with increasing temperature further demonstrating the presence of regime II conditions. The calculated reaction order ranged from 0 to 0.5 and decreased with increasing pressure agreeing well with literature values and trends.     

Spectrophotometric Determination of Phenols and Cyanides After Distillation from Natural Waters

Abstract

Total phenols were determined by molecular spectrophotometry, after distillation, complexation with 4-aminoantipyrine and extraction into chloroform. Cyanides were also determined spectrophotometrically after distillation from the acidified samples, and complexation in moderate acidic solution with barbituric acid. The dynamic ranges were 0 – 100 μg L^?1 for total phenols and 0 – 30 μg L^?1 for cyanides. The above methods were applied in the analysis of river, lake and stream waters collected from Northern Greece. The seasonal and spatial variation of concentrations was evaluated by two-way ANOVA. Background levels (4 – 12 μg L^?1 for total phenols and 0.3 – 3 μg L^?1 for cyanides), were found in almost all surface waters, with some exceptions.     

Alginic acid–silica hydrogel coatings for the protection of osmotic distillation membranes against wet-out by surface-active agents

The formulation of organic–inorganic polymer composites can be used to enhance selected properties, such as susceptibility to microbial attack, thermal stability, mechanical strength and water sorption capability. Accordingly, a series of alginic acid–silica hydrogel films was prepared for testing as protective coating materials for PTFE osmotic distillation membranes. Unprotected hydrophobic membranes are subject to wet-out when contacted by surface-active agents, such as oils and detergents. Films containing 5, 10, 15 and 20 wt.% silica, with and without the addition of glycerol for plasticisation, moisturisation and silica dispersion, were characterised using scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, mechanical strength measurements, and water-swelling measurements. Composites prepared with glycerol addition had better thermal stability, mechanical strength and water sorption capability than those prepared without glycerol addition. Uncoated membranes and membranes coated with composites prepared with glycerol addition were tested for OD performance and resistance to surface-active agents using pure water, orange oil (limonene)–water mixtures, and sodium dodecylbenzene sulfonate detergent solutions. Uncoated membranes showed immediate hydrophobicity loss in the presence of orange oil and detergent. For coated membranes, no wet-out occurred over the 15 h duration of three consecutive 5 h OD trials using orange oil–water mixtures. In the case of detergent solutions, the coating afforded protection to the membrane for 4–5 h. In a separate trial, no wet-out occurred when the coated side of the membrane was placed in contact with 1.2 wt.% orange oil for 72 h.     

Short-cut distillation columns based on orthogonal polynomials of a discrete variable

Increasing competition in the process industries enforces theapplication of mathematical simulation techniques both in thedesign phase and in the operating phase of a plant. A basicapparatus for separation processes is the distillation column.Its rigorous (tray by tray) mathematical modelling results ina system of simultaneous nonlinear equations (algebraic in thesteady-state case, differential-algebraic in the dynamic case).For high (and realistic) numbers of trays and components, thesesystems may become rather large (thousands of equations). Inaddition, realistic plant models often include several distillationcolumns. As a consequence, the numerical solution of these modelsmay become difficult and time-consuming. This has led to attemptsto model the distillation columns less rigorously with the aimof achieving a considerable reduction in the number of equations.The name shortcut distillation columns is common for modelsof this type. The present paper uses a discrete weighted residualmethod for the development of short-cut models. It suggestsa Galerkin method based on orthogonal polynomials in a discretevariable: the tray number. It is a remarkable advantage of thistechnique that even very coarse models satisfy all global balancesexactly.     

Prediction of risers’ tubes temperature in water tube boilers

A dynamic model is developed which enables the prediction of risers’ tubes temperature of water tube boilers under various operating conditions. The model is composed of fluid dynamics model representing the fluid flow in the drum-downcomer-riser loop and a dynamic thermal model of the riser’s temperature. The model gives a detailed account of the two-phase heat transfer process which takes place between the risers’ inner walls and the water–steam mixture flow inside the tubes. The model is used to simulate various operational scenarios of water tube boilers. Results of the simulation provide insight into the dynamic interactions of the boiler’s main variables including the drum pressure, water volume, steam quality and risers’ temperature. Such a model is useful in checking operational scenarios before their actual plant implementation, can be a basis for developing boiler start up procedures and online temperature predictions to prevent eminent tube overheating.