Azeotropes tetrahydrofuran/ethanol

A convincing application of two columns sequence is the split of the azeotrope ethanol (A) / water (B) with tetrahydrofurane (C), as proposed by Stichlmair (1999). Figure 9.19 depicts qualitatively the split sequencing. The entrainer is a low-boiler forming a minimum azeotrope with water (az nbp 64.2 C) below the boiling point of the original water-ethanol azeotrope (azj, nbp 78.2 °C). There is also an azeotrope tetrahydroftirane-ethanol (az, nbp 65.9 C), but this is not essential. Water and ethanol,... 

Tetrahydrofuran, THF, is an important industrial solvent and forms an azeotropic mixture at 5.3 wt% with water (see Table 10.3). To separate water/THF, Li et al. [148] tested the pervaporation performance of different hydrophihc zeolite membranes, zeolite A, zeohte Y, MOR, and ZSM-5. The preliminary test showed that the separation factor increased as the Si/Al ratio of the zeohte decreased, except for the case of zeolite A. This fact is probably due to the lower quality of this membrane with respect to the others since in the permeation of triisopropylbenzene (TIPB), showed the highest flux, 3.1 g/m h, indicating the presence of nonselective defects. Therefore, the best results were obtained with zeolite Y, rendering a separation factor of 300 with a water flux of 2.24 kg/m h at 60°C. The water flux increased with water concentration in the feed, up to a value of 15 wt%, indicating that the zeolite was saturated, as was the same for the case of water/ethanol mixtures in zeolite A, previously described. At the same time, the separation factor decreases as water concentration decreased. The stabihty of the membrane was also studied, showing a stable performance after 35 h of operation. 

The recovery of the waste streams was complex, since a series of azeotropes had to be separated. Different alternatives were simulated and initial cost estimates were made by computer simulation alone. The first simulations were based only on the physical properties incorporated in the software data bank. In a second step additional physical properties mostly liquid liquid equilibrium (LLE) data were measured in order to increase the accuracy of the simulation of the most critical steps. First screening experiments of pervaporation to eliminate water and polar impurities such as methanol and ethanol from the tetrahydrofuran (THF) mixtures were stopped early, as it appeared that the alternatives based on counter current extraction (CCE) and rectification alone were less expensive and probably more robust. The most promising processes were piloted. The pilot experiments allowed confirmation of the results of the simulations and allowed the simulations to be updated to reflect the pilot results. A large part of the work during the pilot experiments was to verify the behaviour of further impurities contaminating the solvents, which had not been taken into account in the first screening. All impurity substances had to be purged efficiently, so that they would not accumulate after repeated recoveries of the solvents. 

Process 2 - Process Description. The impurities in the raw material form azeotropes with tetrahydrofuran and ethylacetate. All the azeotropes had to be separated by a combination of counter current extraction and rectification. The aim was to recover ethylacetate and THF. The following major problems had to be solved by a solvent recovery unit 1) separate the THF/ methanol and the THF/ ethanol azeotropes, 2) dewater the THF and ethylacetate (azeotropes), 3) separate THF (Atmospheric boiling point (Tb) = 65.7°C) from ethylacetate (Tb= 77°C) and methylacetate (Tb = 57.1°C). 

Figure 9.19 Breaking the ethanol-water azeotrope with tetrahydrofurane by a two columns sequence. The process takes place in two distillation regions.

There are many important industrial applications of azeotropic separations, which employ a variety of methods. In this book we discuss several of these chemical systems and demonstrate the application of alternative methods of separation. The methods presented include pressure-swing distillation, azeotropic distillation with a light entrainer, extractive distillation with a heavy entrainer (solvent), and pervaporation. The chemical systems used in the numerical case studies included ethanol-water tetrahydrofuran (THF)-water, isopropanol-water, acetone-methanol, isopentane-methanol, n-butanol-water, acetone-chloroform, and acetic acid-water. Economic and dynamic comparisons between alternative methods are presented for some of the chemical systems, for example azeotropic distillation versus extractive distillation for the isopropanol-water system. 

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