Entrainer azeotropic distillation

The choice of a selective solvent is easier the more the components to be separated differ in their chemical structure. It would be difficult or impossible, for instance, to hnd a selective solvent for the separation of stereoisomers. Nevertheless, the restrictions on extractive distillation solvents are less severe than those on azeotropic distillation entrainers, because the solvent recovery problem is virtually nonexistent due to the wide gap between the boiling points of the solvent and the components to be separated. 

MAJOR USES Used in manufacture of solvents and thinners organic synthesis antiknock agent spectrophotometric analysis determination of octane numbers of fuels azeotropic distillation entrainer. 

In the first class, azeotropic distillation, the extraneous mass-separating agent is relatively volatile and is known as an entrainer. This entrainer forms either a low-boiling binary azeotrope with one of the keys or, more often, a ternary azeotrope containing both keys. The latter kind of operation is feasible only if condensation of the overhead vapor results in two liquid phases, one of which contains the bulk of one of the key components and the other contains the bulk of the entrainer. A t3q)ical scheme is shown in Fig. 3.10. The mixture (A -I- B) is fed to the column, and relatively pure A is taken from the column bottoms. A ternary azeotrope distilled overhead is condensed and separated into two liquid layers in the decanter. One layer contains a mixture of A -I- entrainer which is returned as reflux. The other layer contains relatively pure B. If the B layer contains a significant amount of entrainer, then this layer may need to be fed to an additional column to separate and recycle the entrainer and produce pure B. 

Figure 3.10 A typical azeotropic distillation using an entrainer.

Anhydrous Acetic Acid. In the manufacture of acetic acid by direct oxidation of a petroleum-based feedstock, solvent extraction has been used to separate acetic acid [64-19-7] from the aqueous reaction Hquor containing significant quantities of formic and propionic acids. Isoamyl acetate [123-92-2] is used as solvent to extract nearly all the acetic acid, and some water, from the aqueous feed (236). The extract is then dehydrated by azeotropic distillation using isoamyl acetate as water entrainer (see DISTILLATION, AZEOTROPIC AND EXTRACTIVE). It is claimed that the extraction step in this process affords substantial savings in plant capital investment and operating cost (see Acetic acid and derivatives). A detailed description of various extraction processes is available (237). 

The principle of azeotropic distillation depends on the abiHty of a chemically dissimilar compound to cause one or both components of a mixture to boil at a temperature other than the one expected. Thus, the addition of a nonindigenous component forms an azeotropic mixture with one of the components of the mixture, thereby lowering the boiling point and faciHtating separation by distillation. The separation of components of similar volatiHty may become economical if an entrainer can be found that effectively changes the relative volatiHty. It is also desirable that the entrainer be reasonably cheap, stable, nontoxic, and readily recoverable from the components. In practice, it is probably the ready recoverabiHty that limits the appHcation of extractive and azeotropic distillation. 

Fig. 19. Separation of ethanol and water from an ethanol—water—benzene mixture. Bottoms and are water, B is ethanol, (a) Kubierschky three-column sequence where columns 1, 2, and 3 represent the preconcentration, azeotropic, and entrainer recovery columns, respectively, (b) Material balance lines from the azeotropic and the entrainer recovery columns, A and E, respectively, where represents the overall vapor composition from the azeo-column, 2 1SP Hquid in equiUbrium with overhead vapor composition from the azeo-column, Xj, distillate composition from entrainer...

Introduction The term azeotropic distillation has been apphed to a broad class of fractional distillation-based separation techniques in that specific azeotropic behavior is exploited to effect a separation. The agent that causes the specific azeotropic behavior, often called the entrainer, may already be present in the feed mixture (a self-entraining mixture) or may be an added mass-separation agent. Azeotropic distillation techniques are used throughout the petro-... 

The first three of these are solely X T.E-based approaches, involving a series of simple distillation operations and recycles. The final approach also relies on distillation (X T.E), but also exploits another physical phenomena, liqnid-hqnid phase formation (phase splitting), to assist in entrainer recovery. This approach is the most powerful and versatile. Examples of industrial uses of azeotropic distillation grouped by method are given in Table 13-18. 

The choice of the appropriate azeotropic distillation method and the resulting flowsheet for the separation of a particular mixture are strong functions of the separation objective. For example, it may be desirable to recover all constituents of the original feed mixture as pure components, or only some as pure components and some as azeotropic mixtures suitable for recycle. Not every objective may be obtainable by azeotropic distillation for a given mixture and portfolio of candidate entrainers. 

Exploitation of Homogeneous Azeotropes Homogeneous azeotropic distillation refers to a flowsheet structure in which azeotrope formation is exploited or avoided in order to accomplish the desired separation in one or more distillation columns. The azeotropes in the system either do not exhibit two-hquid-phase behavior or the hquid-phase behavior is not or cannot be exploited in the separation sequence. The structure of a particular sequence will depend on the geometry of the residue curve map or distillation region diagram for the feed mixture-entrainer system. Two approaches are possible ... 

If the azeotrope is not sensitive to changes in pressure, then an entrainer can be added to the distillation to alter in a favorable way the relative volatility of the key components. Before the separation of an azeotropic mixture using an entrainer is considered, the representation of azeotropic distillation in ternary diagrams needs to be introduced. 

Figure 12.33 Separation of isopropyl alcohol (IPA) and water mixture using di-isopropyl ether (DIPE) as entrainer in heterogeneous azeotropic distillation.

Occasionally, a component that already exists in the process can be used as the entrainer, thus avoiding the introduction of extraneous materials for azeotropic distillation. However, in many instances practical difficulties and excessive cost might force the use of extraneous material. 

Wahnschafft OM and Westerberg AW (1993) The Product Composition Regions of Azeotropic Distillation Columns n. Separability in Two-Feed Columns and Entrainer Selection, Ind Eng Chem Res, 32 1108. 

If the system forms azeotropes, then the azeotropic mixtures can be separated by exploiting the change in azeotropic composition with pressure, or the introduction of an entrainer or membrane to change the relative volatility in a favorable way. If an entrainer is used, then efficient recycle of the entrainer material is necessary for an acceptable design. In some cases, the formation of two liquid phases can be exploited in heterogeneous azeotropic distillation. 

Figure 11.44. Azeotropic distillation for the separation of ethanol from water using benzene as entrainer. Compositions are given in mole per cent. E = Ethanol, B = Benzene, W = Water, S = Steam...

Figure 11.45. Composition profile for the azeotropic distillation of ethanol and water, with benzene as entrainer...

Azeotropic Distillation. The concept of azeotropic distillation is not new. The use of benzene to dehydrate ethyl alcohol and butyl acetate to dehydrate acetic acid has been in commercial operation for many years. However, it was only during World War II that entrainers other than steam were used by the petroleum industry. Two azeotropic processes for the segregation of toluene from refinery streams were developed and placed in operation. One used methyl ethyl ketone and water as the azeo-troping agent (81) the other employed methanol (1). 

Future advances in extractive distillation may well follow the same trend as those in azeotropic distillation—that is. where the products can justify the higher processing cost, efficient entrainers will be developed and utilized in commercial operations. 

Figure 13.29. Composition profiles and flowsketches of two azeotropic distillation processes (adapted by King, 1980). (a) Separation of ethanol and water with benzene as entrainer. Data of the composition profiles in the first column were calculated by Robinson and Gilliland, (1950) the flowsketch is after Zdonik and Woodfield (in Chemical Engineers Handbook, McGraw-Hill, New York, 1950, p. 652). (b) Separation of n-heptane and toluene with methylethylketone entrainer which is introduced in this case at two points in the column (data calculated by Smith, 1963).

Keywords Batch distillation Heterogeneous entrainer Azeotropic distillation... 

Azeotropic distillation is appropriate only at high content in aromatics, over 90%. Nonpolar entrainers, such as methanol and acetone, can increase the volatility of nonaromatics by forming low-boiling azeotropes. This method depends strongly on the charge composition, and therefore is not used in industry. 

An important topic in azeotropic distillation regards the purity. This can be managed by means of both entrainer and reflux ratios. For a given purity there is a minimum entrainer ratio that can be determined from a RCM plot. In... 

---