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Abstract

Distillation boundaries originate from saddle azeotropes, dividing the composition space into distillation regions. In heterogeneous mixtures distilled in packed columns, distillation regions overlap. The common area of distillation regions is parametrically sensitive, and it determines the possibilities of crossing (at a finite reflux) the distillation boundaries defined for a total reflux or reboil ratio. This work is an extended research of the paper (Królikowski et al., 2011) conducted to scrutinize whether the distillation regions overlapped in heteroazeotropic systems distilled in staged columns. Presented studies were performed by finding such composition points of the products, for which the rectifying profiles of staged columns were ended in different distillation regions. Calculations were executed for the heterogeneous mixture classified under Serafimov's topological class as 3.1-2: ethanol - benzene - water. Distillation regions for staged columns were found to overlap each other in the heterogeneous systems. As a result, their common part was parametrically sensitive.
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Abstract

Numerical values of the NRTL equation parameters for calculation of the vapour - liquid - liquid equilibria (VLLE) at atmospheric pressures have been presented for 5 ternary mixtures. These values were fitted to the experimental VLLE and vapour - liquid equilibrium (VLE) data to describe simultaneously, as accurately as possible, the VLE and the liquid - liquid equilibria (LLE). The coefficients of this model called further NRTL-VLL were used for simulations of n-propanol dehydration via heterogeneous azeotropic distillation. The calculations performed by a ChemCAD simulator were done for 4 mixtures using hydrocarbons, ether and ester as an entrainer. In majority simulations the top streams of the azeotropic column had composition and temperature similar to the corresponding experimental values of ternary azeotropes. The agreement between the concentrations of both liquid phases formed in a decanter and the experimental values of the LLE was good for all four simulations. The energy requirements were the most advantageous for the simulation with di-npropyl ether (DNPE) and isooctane. Simulations were performed also for one mixture using the NRTL equation coefficients taken from the ChemCAD database. In that case the compositions of the liquid organic phases leaving the decanter differed significantly from the experimental LLE data.
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Abstract

In this work the esterification of diethyl tartrate was studied. The research was focused on the enhancement of reversible reaction yield, which is accomplished by dewatering of the reaction mixture. The removal of water shifts the equilibrium towards the main product. Pervaporation was applied for this purpose, and results were compared to distillation. The advantages and limitations of both processes are discussed. The experimental part consists of dewatering of mixture after the reaction had reached the equilibrium, and was subsequently fed to the test rig equipped with a single zeolite membrane purchased from Pervatech B.V. Results show a significant conversion increase as a result of water removal by pervaporation. Compared to distillation no addition of organics is necessary to efficiently remove water above the azeotrope. Nevertheless, some limitations and issues which call for optimisation are pointed out. A simple numerical model is proposed to support design and sizing of the pervaporation system. Various modes of integrated system operation are also briefly discussed.
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Abstract

The aim of the study was to determine the effect of adding bio-components in the form of methyl esters of corn oil to the milesPLUS diesel oil on its fractional composition. The corn biofuel was produced in-house by using an own-design GW-200 reactor. The diesel fuel evaporated at temperatures ranging from 162 to 352oC. The addition of 7, 20 and 40% of a bio-component in principle does not affect the deterioration of the starting point distillation temperatures. They affect the temperature at the end of distillation to a greater extent, resulting in temperatures exceeding 360oC.
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