1-Butanol binary azeotropes

MgS04, CaO, K2CO3, Ca or solid NaOH, followed by refluxing with, and distn from, calcium, magnesium activated with iodine, aluminium amalgam or sodium. Can also dry with molecular sieves, or by refluxing with n-butyl phthalate or succinate. (For method, see Ethanol.) n-Butanol can also be dried by efficient fractional distn, water passing over in the first fractn as a binary azeotrope (contains about 37% water). An ultraviolet-... 

Since, as examination of Fig. 16.11 shows, it is very easy to strip sec-butanol from water, it will usually be worth doing a recovery and a LLE, using some of the entrainer, on the binary azeotrope feed. 

We examine separation of the mixtures, concentration space of which contains region of existence of two hquid phases and points of heteroazeotropes. It is considerably easier to separate such mixtures into pure components because one can use for separation the combination of distillation columns and decanters (i.e., heteroazeotropic and heteroextractive complexes). Such complexes are widely used now for separation of binary azeotropic mixtures (e.g., of ethanol and water) and of mixtures that form a tangential azeotrope (e.g., acetic acid and water), adding an entrainer that forms two liquid phases with one or both components of the separated azeotropic mixture. In a number of cases, the initial mixture itself contains a component that forms two liquid phases with one or several components of this mixture. Such a component is an autoentrainer, and it is the easiest to separate the mixture under consideration with the help of heteroazeotropic or heteroextractive complex. The example can be the mixture of acetone, butanol, and water, where butanol is autoentrainer. First, heteroazeotropic distillation of the mixture of ethanol and water with the help of benzene as an entrainer was offered in the work (Young, 1902) in the form of a periodical process and then in the form of a continuous process in the work (Kubierschky, 1915). 

Qurishi et al., Ladisch, and Phillips and Humphrey discuss some of the issues concerning the separation of the fermenter products. Doherty and Malone" indicate that a two-column distillation system in conjunction with a decanter can be used to separate the heterogeneous binary n-butanol-water azeotrope. Sticklmair and Faii discuss the separation of the ternary acetone-water-n-butanol system in a two-column system. Pucci et al. suggest that the ternary separation can be achieved in a single column in which a side decanter is used to remove the water. 

The emerging biofuel processes typically have fermentation products that form azeotropes with flie water, which is present in large excess in the fermentor. The most important example is ethanol, which forms a minimum-boiling homogeneous binary azeotrope with water. Butanol is anoflier biofuel example that forms an azeotrope with water. The nonideality in this system is so large that the azeotrope is heterogeneous, forming two liquid phases. 

Such a process depends upon the difference in departure from ideally between the solvent and the components of the binary mixture to be separated. In the example given, both toluene and isooctane separately form nonideal liquid solutions with phenol, but the extent of the nonideality with isooctane is greater than that with toluene. When all three substances are present, therefore, the toluene and isooctane themselves behave as a nonideal mixture and then-relative volatility becomes high. Considerations of this sort form the basis for the choice of an extractive-distillation solvent. If, for example, a mixture of acetone (bp = 56.4 C) and methanol (bp = 64.7°Q, which form a binary azeotrope, were to be separated by extractive distillation, a suitable solvent could probably be chosen from the group of aliphatic alcohols. Butanol (bp = 117.8 Q, since it is a member of the same homologous series but not far removed, forms substantially ideal solutions with methanol, which are themselves readily separated. It will form solutions of positive deviation from ideality with acetone, however, and the acetone-methanol vapor-liquid equilibria will therefore be substantially altered in ternary mixtures. If butanol forms no azeotrope with acetone, and if it alters the vapor-liquid equilibrium of acetone-methanol sufficiently to destroy the azeotrope in this system, it will serve as an extractive-distillation solvent. When both substances of the binary mixture to be separated are themselves chemically very similar, a solvent of an entirely different chemical nature will be necessary. Acetone and furfural, for example, are useful as extractive-distillation solvents for separating the hydrocarbons butene-2 and a-butane. 

Finally, mention should be made of the two effects of interaction of the mathematical model whose negative coefficients show minima of flashpoints for the binary butanol/cyclohexanol and butanol/pentanol combinations. Can they be explained by the presence of azeotropes in these substances The tables examined did not list these mixtures and there was no time to do an experimental check with the students. 

At atmospheric pressure, the n-butanol-water system exhibits a minimum boiling azeotrope and partial miscibility, and hence a binary heterogeneous azeotrope. Figure 1.8 shows the Tyx and Pyx phase diagrams for l-propanol(l)-water(2) azeotropic mixture obtained from the Aspen Plus simulator using the NRTL activity coefficient model. 

The simplest case of combining VLE and LEE is the separation of a binary heterogeneous azeotropic mixture. One example is the dehydration of 1-butanol, a self-entraining system, in which butanol (117.7°C) and water form a minimum-boiling heterogeneous azeotrope (93.0°C). As shown in Eig. 13-69, the fresh feed maybe added... 

Figure 5.2-5 shows equilibrium diagrams for binary systems containing maximum boiling (acetone-chlorofotm) and nunimum boiling (ethanol-water) azeotropes. It also shows an example of an azeotrope which, when condensed, forms two liquid phases (n-butanol-water) this is called a heterogeneous azeotrope. 

When the values of the activity coefficients further increase, two liquid phases can occur, as in the case of the system 1-butanol-water. If the two liquid phase region (shown by the horizontal line) intersect the 45 line in the y-x-diagram, a so-called heterogeneous azeotropic point occurs. In the case of heterogeneous azeotropic points the condensation of the vapor leads to the formation of two liquid phases. In the system 1-butanol-water a butanol-rich and a water-rich phase is formed. The pressure (temperature) and the vapor phase composition show constant values for the binary system in the whole heterogeneous region. 

Dejoz, A. Gonzalez-Alfaro, V. Llopis, F. J.> Vazquez, M. I. Phase equilibria and variation of the azeotropic composition with pressure for binary mixtures of 1-propanol cWorobenzene and 1-butanol -l- chlorobenzene Fluid Phase Equilib. 1998,145, 287-299... 

Water and 1-butanol form a heterogeneous azeotrope and an immiscibility gap over a limited region of ternary compositions exists. The stability of the stationary points of the system and the distillation line map modeled by UNIQUAC are shown on Figure 3a. One distillation boundary, miming from methanol (unstable node) to the binary heteroazeotrope (saddle) divides the composition space in two regions. The system belongs to Serafimov s topological class 1.0-2 (Hilmen, 2002). 

We use the w-butanol-water system in this chapter as an example of this type of binary heterogeneous azeotropic system. A straight-forward two-column distillation system can be used to easily achieve high-purity products. A simple control structure is developed that is capable of handling very large disturbances in throughput and feed composition. The control... 

A simple control stmcture has been developed and demonstrated to be remarkably robust for the separation of the binary heterogeneous azeotropic w-butanol-water system. The process configuration consists of two stripping columns, a decanter, and a single condenser. A tray temperature is controlled in each column. Very large disturbances in feed flowrate and feed composition are effectively handled with product compositions maintamed close to the desired values. 

Influence of the solvent. At a given temperature, the color of the solution depends on the donor properties of the solvent S. Good donors favor the green complex ion, while the red complex is favored by the poor donors. Thermochromism is observed most readily in solvents that are intermediate donors, such as nitriles, ketones and alcohols. Mixtures of a good and a weak donor can also lead to thermochromic behavior. The binary mixtures, nitromethane/ n-butanol (70/30 mol/mol) and isoamyl alcohol/tetrachloroethane (50/50 mol/mol) have been used. Thermochromism is also observed in azeotropic mixtures such as chloroform/methanol and chloroform/ethanol. In these cases, the proportions of the two components do not require adjustment. 

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