DISTILLATION

BASIC DEFINITIONS….
1. Distillation: Separates components by exploiting vapor pressure
differences in liquid mixtures.

2. Bubble Point: The temperature at which the first bubble of vapor forms.

3. Dew Point: The temperature at which the first droplet of liquid condenses

4. Steam Distillation: To separate temperature-sensitive compounds.

Steam lowers the boiling point of components, allowing
separation without thermal degradation
Azeotrope: mixture of two or more components that boil at a constant temperature

with the vapor having the same composition as the liquid.

Azeotropes can be:

o Minimum boiling azeotropes: Boil at a temperature lower than either pure

component (e.g., ethanol-water at 95.6% ethanol).

o Maximum boiling azeotropes: Boil at a temperature higher than either pure

component.
Figure 1: Minimum-boiling azeotropism in the Figure 2: Maximum-boiling azeotropism in the system
system carbon disulfide-acetone: (a) at constant acetone-chloroform: (a) at constant temperature; (b) and (c)
temperature; (b) and (c) at constant pressure. at constant pressure.
 Case Study: Ethanol-Water Mixture
1. Boiling Points:
• Homogeneous solution of ethanol and water o Ethanol: 78.37°C
o Water: 100°C
• Fully miscible due to hydrogen bonding
2. Azeotropic Composition:
• At atmospheric pressure, exhibits azeotropic o At atmospheric pressure, the azeotrope
behavior, forming a minimum-boiling contains ~95.6% ethanol by weight and
boils at 78.1°C.
azeotrope
3. Distillation Strategy:
• Boiling at 78.2°C, ethanol-water mixtures o Rectifying Section: Concentrates
cannot be separated via distillation ethanol.
o Stripping Section: Removes water.
• Widely used in industries as solvents, o Advanced Techniques: Azeotropic
disinfectants, fuels, and beverages distillation or molecular sieves to break
the azeotrope.
 Principles of Distillation
• Distillation separates components based on differences in volatility. The key principle is vapor-liquid
equilibrium (VLE).

1. Vapor-Liquid Equilibrium (VLE):

o In distillation, each component in a liquid has a tendency to evaporate and reach equilibrium with its
vapor phase

o The equilibrium relationship follows Raoult’s Law and Dalton’s Law:

o where:

o yi= Mole fraction of component i in the vapor

o xi= Mole fraction of component i in the liquid

o P = Total system pressure

o 𝑃𝑖∗= Vapor pressure of component i at the system temperature

 o T-x-y diagrams: Temperature vs. composition at constant pressure.

o P-x-y diagrams: Pressure vs. composition at constant temperature.

2. Relative Volatility: Determines the ease of separating components. Higher values indicate
easier separation.

If α>1.5- simple distillation is effective

If α≈1- separation is difficult and requires azeotropic or extractive distillation
 3. Distillation Column Design

• Distillation columns achieve separation via multiple

vapor-liquid contact stages.

1. Types of Columns:

o Tray Columns: Use plates (trays) for vapor-liquid

interaction.

o Packed Columns: Use structured or random

packing to enhance mass transfer.
1. Key Design Parameters:

o Reflux Ratio: Higher reflux improves separation but increases energy consumption.
Reflux ratio = Moles of liquid returned back to column/Moles of distillate product removed
R=L0/D
o Material Balance:
F=D+W
FxF=DyD+WxW
F: Feed
D: Distillate or product (portion that is separated out, usually the lighter component in
distillation)
W: Bottoms or waste (the remaining portion, usually the heavier component in distillation)
o Number of Theoretical Stages: Determined using McCabe-Thiele or Ponchon-Savarit methods.

o McCabe-Thiele Method

Assumptions
 Binary mixture
 The molar flow rates of liquid and vapor remain nearly constant through the column.
 Each stage is assumed to achieve equilibrium between the liquid and vapor phases.

Step 1. Plot the Equilibrium Curve

•The equilibrium curve (y vs. x) represents the vapor-liquid equilibrium (VLE) data for the mixture.
•It is obtained from experimental data or Raoult's Law.
Step 2. Plot the Operating Lines
The column is divided into two sections:
•Rectifying section (above the feed stage): The vapor is enriched with the more volatile
component.
•Stripping section (below the feed stage): The remaining liquid is enriched with the less volatile
component.
a) Rectifying Section Operating Line (ROL):

•R = L/D (Reflux Ratio: ratio of liquid returned to the column to the distillate product).
•xD: Composition of the distillate.
b) Stripping Section Operating Line (SOL):

•Ls/Vs: Ratio of liquid to vapor in the stripping section.

•xW: Composition of the bottoms product.
•The SOL meets the ROL at the q-line intersection.

c) Feed Line (q-line):

q: Quality of the feed

(Determines how much of the feed is vaporized)

Step 3. Step Off Stages Graphically

• Start at (xD, xD) and move horizontally to the ROL
• Move vertically to the equilibrium curve (represents phase equilibrium)
• Repeat the process (stepping method) until reaching xW at the bottom section
• The number of steps corresponds to the number of equilibrium stages
 o Column Diameter: Sized based on vapor flow rate and flooding velocity.

o The Souders-Brown Equation

•where:
•dc = Column diameter
•V = Volumetric vapor flow rate
•Uf= Allowable flooding velocity (typically 80% of the actual flooding velocity)
•The flooding factor (FF), usually around 0.8 to 0.85, ensures the column operates below the
flooding point.
•Higher vapor flow rates require a larger column diameter to prevent flooding and ensure
stable vapor-liquid contact.
1. Efficiency Metrics:
o Murphree Tray Efficiency: Evaluates single tray performance.

•yactual = Actual vapor composition leaving the tray

•yinlet = Composition of vapor entering the tray
•yequilibrium = Theoretical equilibrium composition

o Overall Column Efficiency (Eoc): Accounts for inefficiencies across the column.
o Represents the entire column's performance
 ENERGY CONSIDERATIONS

•Reboiler provides heat to generate vapor.

•Condenser removes heat to liquefy the vapor.

•Reflux improves separation by returning liquid to the column.

•Minimum Reflux Ratio: Found using the intersection of operating lines at the pinch point.

•Total Reflux: Maximum separation but infinite trays required.

 STEAM DISTILLATION

• For temperature-sensitive compounds

• Steam is introduced into the system, reducing the boiling point of the components
• Immiscible liquids form a system where the total vapor pressure is the sum of the individual
partial pressures
• Reduces the boiling point significantly below that of the individual components, minimizing
thermal degradation
Advantages
 Reduces thermal degradation
 Simplifies separation of immiscible liquids

Design Considerations

 Steam flow rate must be optimized

 Efficient condensation is crucial for vapor recovery
Applications of Distillation

Petroleum refining (fractionation of crude oil)

Ethanol production (separation of ethanol from water)

Chemical processing (purification of solvents and reactants)

Air separation (cryogenic distillation of oxygen, nitrogen)