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Distillation: Fundamentals and Processes

1. Introduction
Distillation, often referred to as rectification in Europe, is the most important technique for separating fluid
mixtures in process industries, accounting for approximately 95% of all liquid separations. Its exceptional
role is due to its ability to fractionate a fluid mixture into all constituents. However, distillation has
disadvantages, including a risk of thermal degradation of the species and a high energy demand.

2. Principles of Distillation
The distillation process is based on a simple principle consisting of three steps: (1) generation of a
two-phase system, (2) mass transfer across the interface, and (3) separation of the two phases. This
principle is also applied to other separation processes such as absorption, adsorption, and extraction.
However, unlike these processes, distillation generates the two-phase system (vapor-liquid) by the supply
of heat, which can easily be removed later.

3. History of Distillation
Distillation is an ancient technique pioneered by chemists in Alexandria in the first century AD. It was
first used in northern Italy for the production of alcoholic beverages around the eleventh century. The
development of distillation equipment was significantly influenced by this field of application.

4. Distillation Equipment
A typical distillation unit consists of a reboiler, oven, coolers, receiver, headpiece, and condenser. The
reboiler supplies heat to the liquid in the oven, generating vapor that is condensed in coolers. The
condensate drips into the receiver, and the process is named after the Latin word 'destillare' (dripping
or trickling down).

5. Rectification
Rectification refers to a process by which the concentration of a substance is further increased after the
first distillation step. The term is derived from the Latin words 'recte facere,' meaning rectify or improve.
In a distillation unit shown in Figure 1, two sequential distillation steps are performed simultaneously.
The product of the first distillation is fed into the headpiece of the equipment, called the rectification,
which is heated by the vapor rising up from the reboiler. The vapor produced is condensed in the coolers,
and a liquid product with a higher alcohol concentration is collected in a second receiver.

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6. Vapor-Liquid Equilibrium
In a single-component system, the vapor pressure is an exponential function of temperature. In multi-com-
ponent systems, however, boiling points and dew points constitute separate lines in the pressure-temper-
ature diagram. The region of two coexistent phases is located between these two lines, and this is caused
by different concentrations in the coexistent phases.

7. Distillation Calculations
Distillation calculations involve the use of diagrams that plot the concentration of the vapor versus the
concentration of the liquid. Such diagrams are important in distillation processes. In extremely non-ideal
mixtures, the equilibrium curves intersect the diagonal of the y-x diagram. At the point of intersection,
vapor and liquid have the same concentration, called an azeotrope, which is of great importance to
distillation as it constitutes a barrier to separation.

8. Ideal and Non-Ideal Systems

In ideal systems, both temperatures monoton Q decrease with rising concentrations of the low boiler.
In non-ideal systems, however, boiling and dew point temperatures can show different behaviors due to
intermolecular forces. The smaller the concentration of a component, the bigger or smaller its activity
coefficient, depending on whether intermolecular forces are repulsive or attractive, respectively.

9. Real Systems
Many liquid mixtures encountered in industrial practice exhibit non-ideal equilibrium behavior. In
high-pressure systems, both the vapor phase and the liquid phase can deviate from Dalton’s and Raoult’s
laws. Corrections of Dalton’s law are made by substituting pressures p by fugacities f. Correlations of the
fugacity coefficient ji are made using the law of corresponding states first developed by Van der Waals.

10. Distillation Processes

Distillation processes include single-stage distillation, multi-stage distillation (rectification), and batch
distillation. In single-stage distillation, vapor and liquid are in intimate contact throughout the apparatus,
and the final vapor fraction is in equilibrium with the final liquid fraction. In open distillation, vapor
fractions are steadily removed from the liquid in the apparatus, resulting in a higher concentration of low
boiler in the vapor product. In counter-current distillation, vapor and liquid flow in opposite directions
through the apparatus, resulting in the highest concentration of the vapor product.

11. Multi-Stage Distillation (Rectification)

Rectification is a multiple distillation process in which several sequential distillation steps are arranged in a
vertical cascade with counter-current flow of vapor (upward) and liquid (downward). Each stage is directly
heated by the vapor from the previous stage. Such processes are technically realized in counter-current

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columns. The starting mixture is continuously fed into the middle of the column and split into an overhead
fraction (distillate) and a bottom fraction (bottoms) having different concentrations. The upper part of the
column is called the rectifying section, and the lower part is called the stripping section. The products are
continuously withdrawn from the top and bottom of the column. By supply of heat, part of the bottoms is
evaporated and recycled into the bottom of the column (vapor reboil). Analogously, part of the distillate is
recycled into the top of the column (liquid reflux). This product recycling is essential for the separation.
Column internals provide an intimate contact between the two phases and, in turn, a good interfacial mass
transfer. Thus, the light components enrich in the vapor phase and move with it towards the top of the
column. Analogously, the heavy components enrich in the liquid phase and proceed downwards with the
liquid flow. As a result, the distillate is rich in low boiling components, and the bottoms are rich in high
boiling components.

12. Binary Mixtures

By convention, the concentrations x, y, and z refer to the low boiling component in binary mixtures.
Material balances around the column formulate a relationship between amounts and concentrations of
the products. The thermodynamics of binary distillation processes are calculated with the aid of the
McCabe-Thiele diagram, in which the molar concentration y of the vapor is plotted versus the molar
concentration x of the liquid. The actual states of vapor and liquid coexistent at any cross section of the
column constitute the operating lines. The distance between the operating and equilibrium lines represents
the driving force for the interfacial mass transfer. Operating lines always lie in the region between the
equilibrium line and the diagonal of the McCabe-Thiele diagram. They end at their intersections with the
diagonal. The stages (equilibrium stages, theoretical stages) drawn between operating and equilibrium
lines are a quantitative measure for the difficulty of the separation.

13. Reflux and Reboil Ratios

The reflux of liquid at the top of the column and the reboil of vapor at the bottom of the column are
essential prerequisites for the separation effect of the column. There are two extreme cases of reflux
and reboil ratios: total reflux (or total reboil) and minimum reflux (or minimum reboil). The minimum
reflux ratio is the minimum liquid reflux required to obtain a desired separation. The energy demand of
a distillation column is directly dependent on the reflux and reboil ratios.

14. Ternary Mixtures

The principles of binary distillation are also valid in multi-component distillation. However, there are some
significant new features in multi-component distillation. Ternary mixtures constitute the first general case
of distillation. The fundamentals of ternary distillation have to be explained in detail.

15. Multi-Component Mixtures

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As in ternary systems, either the low boiling or the high boiling component can be recovered in a single
column from a zeotropic multi-component mixture. Thus, total fractionation of such mixtures requires
several distillation columns in line. The thermodynamic calculation of multi-component distillation is
performed with rigorous simulation models based on the so-called MESH equations.

16. Batch Distillation (Multi-Stage)

Batch distillation is a discontinuous form of distillation processes. It is characterized by the coupling of
a liquid vessel, into which the mixture is initially charged, with a distillation column, from which the
products are continuously withdrawn. Three different configurations of batch distillation processes are
shown in Figure 33.

17. Reactive Systems

Important applications of batch distillation are systems with reversible liquid-phase reactions. Processes
with reactions that take place in the vessel can be treated with the methods outlined in the previous section.
The process configurations have to be adjusted to the reaction at hand. The reactants have to remain in
the vessel, and only the products should be separated by the column. By removing the products from the
reaction zone in the vessel, a complete conversion into the products can be established even in reversible
reactions.

18. Reactive Distillation

Reactive distillation (or catalytic distillation) is the simultaneous realization of a chemical reaction and a
distillative separation in a counter-current column. This process is advantageously used in the production
of fine and specialty chemicals, pharmaceuticals, and biofuels.

19. Energy Demand

The energy demand of a distillation column is described either by the heat required for evaporation at the
bottom or for condensation of the vapor at the top of the column. The most important feature of distillation
is the energy demand of the column. It is described either by the heat required for evaporation at the bottom
or for condensation of the vapor at the top of the column.

20. Conclusion
Distillation is a fundamental separation process in the chemical industry. Its principles, equipment, and
processes have been developed and refined over centuries. Today, distillation is used in a wide range of
applications, from the production of alcoholic beverages to the separation of complex mixtures in the
chemical and pharmaceutical industries. Despite its long history, distillation continues to be an active
area of research and development, with new technologies and processes being developed to improve its
efficiency, selectivity, and sustainability.

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