Chapter 1.

1: Distillation and Related

Concepts

Principle of Distillation

Distillation is a fundamental separation method in chemical engineering, based on

differences in the volatilities of components in a boiling liquid mixture. The process
involves several key steps:

1. Heating a liquid mixture to create vapor:

- Energy is supplied to increase the temperature of the mixture
- More volatile components begin to vaporize at lower temperatures
- Example: In crude oil distillation, light hydrocarbons like butane and propane
vaporize first

2. Condensing the vapor back into liquid:

- Vapor rises and contacts a cooler surface
- Heat transfer occurs, causing the vapor to condense
- Example: In a traditional pot still used for whiskey production, vapor condenses in
the neck and Lyne arm

3. Collecting the separated components:

- More volatile components are collected at the top of the column
- Less volatile components remain at the bottom
- Example: In petroleum refining, lighter fractions like gasoline are collected near the
top, while heavier components like diesel and residual fuel oil are drawn from lower
sections

Key points to remember:

- More volatile components vaporize first due to their lower boiling points
- Less volatile components remain in liquid state longer, requiring higher temperatures
to vaporize
- Repeated vaporization and condensation increase purity by creating multiple
equilibrium stages
- The efficiency of separation depends on factors such as the number of theoretical
plates, reflux ratio, and operating conditions

Applications of Distillation

Distillation is widely used in various industries:

1. Petrochemical:
 - Crude oil fractionation to produce gasoline, diesel, kerosene, and other fuels
- Separation of individual hydrocarbons like ethylene and propylene

2. Beverage:
- Production of alcoholic spirits such as whiskey, vodka, and rum
- Concentration of fruit juices and essential oils

3. Pharmaceutical:
- Purification of active ingredients like antibiotics
- Solvent recovery in drug manufacturing processes

4. Water treatment:
- Desalination of seawater for drinking water production
- Purification of industrial process water

5. Chemical:
- Separation of organic compounds like benzene and toluene
- Production of high-purity chemicals for semiconductor industry

6. Air separation:
- Production of nitrogen, oxygen, and argon from liquefied air

7. Biofuel production:
- Purification of bioethanol from fermentation broths

Raoult's Law

Raoult's Law is a fundamental principle in vapor-liquid equilibrium, describing the

relationship between vapor pressure of components in an ideal mixture:

P(i) = x(i) * P°(i)

Where:
- P(i) = Partial pressure of component i in the vapor phase
- x(i) = Mole fraction of component i in the liquid phase
- P°(i) = Vapor pressure of pure component i at the same temperature

Implications of Raoult's Law:

1. The vapor pressure of a component in a mixture is directly proportional to its mole

fraction in the liquid phase.
2. As the concentration of a component increases, its contribution to the total vapor
pressure increases linearly.
3. Raoult's Law assumes ideal behaviour, which is often a good approximation for
mixtures of similar molecules.
Example calculation:
Consider a mixture of benzene (A) and toluene (B) at 80°C, where:
- x(A) = 0.6, x(B) = 0.4
- P°(A) = 100 kPa, P°(B) = 40 kPa

Using Raoult's Law:

P(A) = 0.6 * 100 kPa = 60 kPa
P(B) = 0.4 * 40 kPa = 16 kPa
Total pressure = 60 + 16 = 76 kPa

Deviations from Raoult's Law:

Real mixtures may deviate from Raoult's Law due to:

- Molecular interactions between different components
- Formation of azeotropes
- Presence of ionic species

Examples of deviations:
1. Positive deviation: Mixture of ethanol and cyclohexane
- Total vapor pressure is higher than predicted by Raoult's Law
- Indicates weaker interactions between unlike molecules

2. Negative deviation: Mixture of chloroform and acetone

- Total vapor pressure is lower than predicted by Raoult's Law
- Indicates stronger interactions between unlike molecules

3. Azeotropes: Ethanol-water mixture

- Forms a constant boiling mixture at 95.6% ethanol by weight
- Cannot be separated further by simple distillation

Dalton's Law

Dalton's Law, also known as Dalton's Law of Partial Pressures, states that the total
pressure of a gas mixture is the sum of the partial pressures of individual components:

P(total) = P(1) + P(2) + ... + P(n)

Where P(i) is the partial pressure of component i

Applications of Dalton's Law in Distillation:

1. Vapor composition calculation:

- The mole fraction of a component in the vapor phase can be calculated as y(i) = P(i) /
P(total)
 - Example: In a binary mixture of methanol and water, if P(methanol) = 40 kPa and
P(total) = 100 kPa, then y(methanol) = 40/100 = 0.4

2. Total pressure control:

- In vacuum distillation, the total pressure is reduced to lower boiling points
- Example: Distillation of temperature-sensitive compounds like vitamins or
fragrances

3. Multi-component distillation:
- Dalton's Law helps in understanding the behaviour of each component in complex
mixtures
- Example: In petroleum refining, where multiple hydrocarbon components are
present

4. Design of condensers and reboilers:

- Calculation of heat transfer requirements based on partial pressures
- Example: Sizing a condenser for a methanol-water distillation column

Azeotropes

Azeotropes are mixtures that have the same composition in liquid and vapor phases at a
certain pressure. This phenomenon complicates the separation process in distillation.

1. Minimum boiling azeotropes:

- Boil at a temperature lower than either pure component
- Example: Ethanol-water mixture (95.6% ethanol by weight)
- Characteristics:
* Cannot be separated by simple distillation
* Require special techniques like azeotropic distillation or pressure-swing distillation
- Other examples:
* Isopropanol-water (87.7% isopropanol)
* Acetone-chloroform (64.7% acetone)

2. Maximum boiling azeotropes:

- Boil at a temperature higher than either pure component
- Example: Nitric acid-water mixture (68% nitric acid by weight)
- Characteristics:
* Also, cannot be separated by simple distillation
* May require extractive distillation or other advanced techniques
- Other examples:
* Hydrochloric acid-water (20.2% HCl)
* Formic acid-water (77.5% formic acid)

3. Ternary azeotropes:
- Involve three components
- Example: Ethanol-water-benzene system
- Used in azeotropic distillation to break binary azeotropes
Dealing with Azeotropes:

1. Pressure-swing distillation:
- Exploits the pressure dependence of azeotropic composition
- Involves alternating between high- and low-pressure distillation
- Example: Separation of acetone-methanol mixture

2. Extractive distillation:
- Adds a third component (solvent) to break the azeotrope
- The solvent alters the relative volatility of the original components
- Example: Using ethylene glycol to separate ethanol-water mixture

3. Reactive distillation:
- Combines chemical reaction with distillation
- Can potentially overcome azeotropic limitations
- Example: Production of methyl acetate from methanol and acetic acid

4. Azeotropic distillation:
- Adds a third component to form a ternary azeotrope
- Allows separation of the original binary mixture
- Example: Using benzene to separate ethanol-water mixture

5. Membrane distillation:
- Uses a hydrophobic membrane to selectively permeate vapor
- Can potentially separate azeotropic mixtures
- Example: Dehydration of isopropanol-water mixture

Multi-component Systems

Multi-component systems involve more than two components in a mixture. These

systems are more complex and present unique challenges in separation processes.

Key points:
- More complex separation processes due to interactions between multiple components
- May require multiple distillation columns arranged in series or parallel
- Often use advanced techniques like extractive distillation or divided wall columns

Challenges in Multi-component Distillation:

1. non-ideal behaviour:
- Deviations from Raoult's Law become more significant
- Interactions between different molecules affect vapor-liquid equilibrium
- Example: Separation of aromatic hydrocarbons (benzene, toluene, xylenes)
2. Multiple azeotropes:
- Possibility of forming binary or ternary azeotropes
- Complicates separation strategy
- Example: Ethanol-isopropanol-water system

3. Energy efficiency:
- Separating multiple components often requires more energy
- Optimization becomes crucial for economic viability
- Example: Crude oil distillation, where energy integration is essential

4. Product purity and recovery:

- Achieving high purity for all components simultaneously can be challenging
- Trade-offs between purity and recovery must be considered
- Example: Separation of close-boiling isomers in petrochemical industry

Advanced Techniques for Multi-component Distillation:

1. Divided wall columns:

- Single column shell with internal partitions
- Can achieve the separation of three or more components in one unit
- Example: Separation of aromatics (benzene, toluene, xylenes) in petrochemical
industry
- Advantages:
* Reduced energy consumption (up to 30%)
* Lower capital costs
* Smaller footprint

2. Heat integrated distillation columns:

- Utilize heat integration to improve energy efficiency
- Examples include petlyuk columns and thermally coupled distillation
- Case study: Separation of propylene-propane-ethane mixture
* Energy savings of up to 40% compared to conventional sequences

3. Hybrid processes:
- Combine distillation with other separation techniques
- Examples include extraction-distillation and absorption-distillation
- Application: Recovery of acetic acid from aqueous solutions
* Liquid-liquid extraction followed by distillation
* Improves separation efficiency and reduces energy consumption

4. Pressure-swing distillation for multi-component systems:

- Exploits pressure dependence of relative volatilities
- Example: Separation of cyclohexane-benzene-toluene mixture
- Advantages:
* Can separate mixtures with multiple azeotropes
* Potentially lower energy consumption than conventional methods

5. Advanced control strategies:

 - Model predictive control (MPC) for optimizing multi-component distillation
- Real-time optimization based on economic objectives
- Example: Control of naphtha splitter in refinery operations
* Improves product quality and energy efficiency

Flash Distillation

Flash distillation, also known as equilibrium distillation or flash vaporization, is a

single-stage separation process. It's often used as a preliminary separation step or in
processes where high purity is not required.

Process steps:
1. Feed mixture is heated to a predetermined temperature
2. Pressure is reduced, causing partial vaporization of the mixture
3. Vapor and liquid phases are separated in a flash drum
4. Composition differs between phases due to relative volatilities of components

Applications of Flash Distillation:

1. Crude oil stabilization:

- Removes light hydrocarbons to reduce vapor pressure
- Example: Stabilization of crude oil before storage or transportation
- Typical operating conditions:
* Temperature: 35-50°C
* Pressure: 700-1000 kPa

2. Natural gas processing:

- Separates heavier hydrocarbons from methane
- Example: Removal of natural gas liquids (NGLs) from raw natural gas
- Typical operating conditions:
* Temperature: -20 to -40°C
* Pressure: 4000-6000 kPa

3. Steam generation:
- Produces steam from boiler feed water
- Example: Flash steam recovery in industrial processes
- Typical operating conditions:
* Pressure reduction from high-pressure condensate to atmospheric pressure

4. Solvent recovery:
- Separates volatile solvents from non-volatile solutes
- Example: Recovery of acetone from polymer solutions
- Advantages:
* Simple operation
* Low capital cost
5. Desalination:
- Multi-stage flash distillation for seawater desalination
- Example: Large-scale desalination plants in Middle Eastern countries
- Typical operating conditions:
* Top brine temperature: 90-120°C
* Number of stages: 20-40

Equilibrium Relationship in Flash Distillation:

The key equation for flash distillation is:

F * z(i) = V * y(i) + L * x(i)

Where:
- F = Feed rate
- V = Vapor rate
- L = Liquid rate
- z(i) = Mole fraction of component i in feed
- y(i) = Mole fraction of component i in vapor
- x(i) = Mole fraction of component i in liquid

This equation, combined with vapor-liquid equilibrium relationships, allows for the
calculation of compositions and flow rates in flash distillation.

Example calculation:
Consider a binary mixture of propane (A) and butane (B) with feed composition z(A) =
0.6, z(B) = 0.4. If 40% of the feed vaporizes (V/F = 0.4), and the equilibrium constant
K(A) = 2.5, K(B) = 1.0, determine the compositions of vapor and liquid phases.

Solution:
1. Use K-values to relate x(i) and y(i): y(i) = K(i) * x(i)
2. Substitute into material balance: F * z(i) = V * K(i) * x(i) + L * x(i)
3. Solve for x(i) and y(i)

Results:
x(A) = 0.48, x(B) = 0.52
y(A) = 1.20, y(B) = 0.52

Normalized vapor composition:

y(A) = 0.70, y(B) = 0.30

This example demonstrates how flash distillation can achieve a significant separation in
a single stage, with the vapor phase enriched in the more volatile component (propane).

Continuous Distillation with Reflux

Continuous distillation with reflux is the most common industrial distillation process,
offering higher separation efficiency compared to simple or flash distillation.

Key features:
1. Feeding the mixture continuously into the column
2. Partial condensation of vapor at the top (reflux)
3. Returning part of the condensate to the column
4. Withdrawing products continuously (distillate and bottoms)

Reflux Ratio:

The reflux ratio (R) is a crucial parameter in continuous distillation:

R=L/D

Where:
- L = Liquid flow rate returned to the column
- D = Distillate flow rate

Higher reflux ratios generally lead to better separation but require more energy.

Example:
Consider a distillation column separating a mixture of benzene and toluene. The column
operates with a distillate flow rate of 100 kg/h and a reflux flow rate of 300 kg/h.

Reflux ratio = 300 / 100 = 3

This means that for every 1 kg of distillate produced, 3 kg of liquid is returned to the
column as reflux.

Effects of reflux ratio:

- Low reflux ratio (e.g., R = 0.5):
* Lower energy consumption
* Reduced separation efficiency
* Smaller column diameter required
- High reflux ratio (e.g., R = 5):
* Higher energy consumption
* Improved separation efficiency
* Larger column diameter required