Azeotropic Mixtures and Their Separation: Important Issues and Design Procedures FIRST SEMESTER 2012-2013, BITS C421T/C422T

THESIS Outline for the Presentation:

What is Azeotropy? The term azeotrope means non-boiling by any means (Greek: a-non, zeo-boil, tropo-way/mean), and denotes a mixture of two or more components where the equilibrium vapor and liquid compositions are equal at a given pressure and temperature. More specifically, the vapor has the same composition as the liquid and the mixture boils at a temperature other than that of the pure components boiling points. Azeotropes have sometimes been mistaken for single components because they boil at a constant temperature. However, for an azeotrope a change in pressure changes not only the boiling temperature, but also the composition of the mixture, and this easily differentiates it from a pure component. If at equilibrium temperature the liquid mixture is homogenous, i.e., one liquid phase and one vapor phase then the azeotrope formed is a homo-azeotrope. Whereas if at equilibrium temperature the vapor phase coexists with two liquid phases, it is then considered a hetero-azeotrope.

At moderate to low pressures and temperatures away from the critical point, the vapor-liquid phase equilibrium for a multicomponent mixture may be expressed as: yi P = xi i (T, x) Pisat (T),
i

= 1, 2, 3, .., n

where yi and xi are the vapor and liquid compositions of component i respectively, P and T are the system temperature and pressure, i is the activity coefficient of component i in the liquid phase. Pisat is the vapor pressure of component i. Activity coefficient is a measure of the non-ideality of a mixture and changes both with temperature and composition. When the activity coefficient = 1, the mixture is then said to be ideal and the equation is simplified to Raoults law. yi P = xi Pisat (T),
i

= 1, 2, 3, .., n

For non-ideal mixtures the value of i can either be greater than 1(>1), i.e. a positive deviation from Raoults law, or less than 1(<1), i.e. a negative deviation from Raoults law The particular deviation from an ideal state is determined by the balance between the physiochemical forces between different or identical components. These are in short classified into three groups: 1) Positive deviation from Raoults law: Different molecules repel each other, or in other words, the attraction between identical molecules (A-A and BB) is stronger than between different molecules (A-B). This may lead to the formation of a minimum-boiling azeotrope (homogeneous). If the deviation is very large it may cause heterogeneity. 2) Negative deviation from Raoults law: Different molecules attract each other, or in other words, the force of intermolecular attraction (i.e. between different molecules) is the strongest. This may lead to the formation of a maximum-boiling azeotrope (homogeneous). 3) Ideal mixture obeys the Raoults law: The components have similar physiochemical properties. The intermolecular forces between different and identical molecules are the same or equal.

Here is a brief introduction of the current various separation methods used to separate azeotropic mixtures: Extractive distillation: In this method we use a large amount of a relatively high-boiling solvent to alter the liquid-phase activity coefficients of the mixture, so that the relative volatilities of the key components become more favorable. The solvent enters the column above the feed tray and a few trays below the top, and exits from the bottom of the column without causing the formation of an azeotrope with the bottom product. High-purity products are produced from the top of the extractive column. Salt distillation: this is a variation of extractive distillation, difference being, the relative volatilities of the key components is altered by dissolving a soluble, ionic salt in the top reflux. Because the salt is non-volatile, it stays in liquid phase as it passes down the column. Pressure-Swing distillation: if the composition of the azeotrope changes significantly with change in pressure, two columns operating at two different pressures can be used to achieve this separation. Homogeneous Azeotropic distillation: a method of separating a mixture by adding an entrainer that forms a homogeneous maximum or minimum

azeotrope with one or more feed components. The entrainer is added near top of the column, to the feed, or near the bottom of the column, depending upon whether the azeotrope is removed from the top or bottom. Heterogeneous Azeotropic distillation: a more useful Azeotropic distillation method in which a minimum-boiling heterogeneous azeotrope is formed by the entrainer. The azeotrope splits into two liquid phases in the overhead condensing system. One liquid is sent back as reflux to the column while the other is removed as product or sent to another separation step. Reactive distillation: this method adds a separating agent to react selectively or reversibly with one or more of the constituents of the feed. The reaction product is subsequently distilled from the non-reacting components. The reaction is then reversed to recover the separating agent and other reacting components. Reactive distillation also refers to the case where a chemical reaction and multistage distillation are conducted simultaneously in the same apparatus to produce other chemicals. This combined operation is also referred to as catalytic distillation if a catalyst is used. This is suited for chemical reactions that limited by equilibrium constraints, since one (or more) of the products of the reaction is (are) continuously separated from the reactants. Another alternative technique for separating homo-azeotropes, such as membrane separation, usually combined with distillation. These systems are referred to as hybrid distillation systems (augmenting distillation with complementary separation technologies).

Membrane-distillation hybrids
The use of membranes as separating agents is a fast growing and developing field. The industrial applications were of this methods were greatly accelerated in the 1980s (Seader and Henley, 1998). In this method the membrane itself acts as mass separating agent, selectively absorbing and diffusing one of the azeotrope-forming components. The feed mixture is separated partially by means of a semi-permeable membrane into a retentate, which is the part of the feed that does not pass through the membrane, and, permeate, the part of the feed mixture that passes through the membrane. Pervaporation: Some characters the membrane must have, was given by Seader and Henley (1998): It must have good permeability (high mass-transfer flux)

High selectivity Stability Freedom from fouling (detect-free) Long life (two years or more)

Fig: Separation of binary homoazeotropic mixtures by membranedistillation hybrids. (a) pervaporation unit between two distillation columns; (b) distillation column augmented with a vapor permeation unit where the retentate has sufficient purity to be a final product.

Pressure-swing distillation: As we already know, pressure changes can have a great effect on the vaporliquid equilibrium compositions of azeotropic mixtures. By decreasing or increasing the operating pressure of individual columns we can move the distillation boundaries in the composition space to make azeotropes appear or disappear (or transform into heteroazeotropes). For some mixtures, the pressure change of the column can result in a significant change in the azeotrope composition and cause a complete separation by pressure swing distillation (as shown in the figure below)

Fig: Pressure-swing distillation: (a) temperature-composition diagram for a minimum-boiling azeotrope (binary) that is sensitive to changes in pressure; (b) the possible distillation sequence for the system.

Entrainer-Addition Distillation Methods

In general we call a distillation method where the addition of a component to the feed mixture in the column facilitates the separation of the mixture into its components. We call the mixture to be separated as original mixture, and the added component that facilitates the separation as the entrainer. For the purpose of understanding and ease of visualization, we limit our considerations to binary azeotropes and one-component entrainers. We distinguish between 3 different conventional entrainer-addition distillation methods depending on the properties and role of the entrainer and the scheme of the process: Homogeneous azeotropic distillation (ordinary distillation of homoazeotropes): The distillation is carried out in a conventional single-feed column. The entrainer is completely miscible with the components of the original mixture (it may form homoazeotropes with the original mixture components). Heteroazeotropic distillation (decanter-distillation hybrids that involve heteroazeotropes): The distillation is carried out in a combined column and decanter system. The entrainer is forms a heteroazeotrope with at least one of the components of the original mixture. Extractive distillation:

 The main part of the entrainer is removed as the bottom product. The distillation is carried out in a two-feed column where the entrainer is introduced above the original feed mixture point. The entrainer has a boiling-point that is substantially higher than the original mixture components and is selective to one of the components. Extractive distillation at the broader definition is what we are actually interested in, this includes the symmetrical process of separating maximum-boiling type azeotropes using a low boiling entrainer (re-extractive distillation), and combined heteroazeotropic and extractive distillation schemes (heteroazeotropic distillation). There are many other methods which are also considered entraineraddition distillation methods, they are: Reactive distillation (the entrainer reacts preferentially and reversibly with one of the original mixture components). Chemical drying (chemical action and distillation) and distillation in the presence of salts.