TCN3132 Separation Processes

Lecture 1: Basics of Equilibrium and

Introduction to Flash Distillation

Dr Suraj Vasudevan
Email: [email protected]

Department of Chemical &

Biomolecular Engineering

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 1

 Overview

• Equilibrium in separation processes

 Vapor-liquid equilibrium
 Vapor pressure and Raoult’s law
 Distribution coefficient
 Binary phase diagrams
 Relative volatility Reference:
Wankat 3rd edition
Chapters 1 and 2
• Flash distillation
 Schematic, nomenclature and the problem

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 2

 Phase Equilibrium
• Consider a two-component system
• A and B will condense and vaporize at different rates
• At equilibrium, the rate at which each species condenses is
the same as the rate at which it vaporizes
 The temperatures, pressures and fractions of the two
phases are constant
• Thermal equilibrium
 𝑇𝑇𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 = 𝑇𝑇𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉
• Mechanical equilibrium
A two-component two-phase
 𝑃𝑃𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 = 𝑃𝑃𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉 system at equilibrium
• Chemical equilibrium
 𝜇𝜇𝑖𝑖 𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿𝐿 = 𝜇𝜇𝑖𝑖 𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉𝑉

Where 𝜇𝜇 = chemical potential

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 3

 Vapor-Liquid Equilibrium
• We need at least two phases to separate mixtures
 Vapor/gas – liquid
 Liquid – liquid
• Vapor versus gas
 Gas to the left of point B is below critical temperature
and is called vapor
 Vapor can be condensed to liquid by compression at
constant temperature or by cooling at constant pressure
• Curve AB is the vapor pressure of the liquid at the
P-T diagram of water
corresponding temperatures
 Every liquid has vapor pressure and boils when vapor
pressure is equal to the external pressure
 At all conditions corresponding to points on this curve,
liquid and vapor co-exist in equilibrium, and is called
saturated liquid and saturated vapor respectively
VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 4
 Vapor Pressure Data Raoult’s Law
• Vapor pressure data as a function of • For ideal liquid and ideal vapor mixture:
temperature is widely available for common  𝒙𝒙𝒊𝒊 𝑷𝑷𝒊𝒊 𝟎𝟎 = 𝒚𝒚𝒊𝒊 𝑷𝑷𝑻𝑻 = 𝑷𝑷𝒊𝒊 where 𝑃𝑃𝑖𝑖 is partial
liquids pressure of component i in vapor phase and
• Vapor pressure for a component (𝑃𝑃𝑖𝑖 0 ) can be 𝑃𝑃𝑇𝑇 is total pressure of the system
calculated from Antoine’s equation: • Rearranging Raoult’s law:
0
 𝑙𝑙𝑜𝑜𝑜𝑜𝑃𝑃𝑖𝑖 = 𝐴𝐴𝑖𝑖 −
𝐵𝐵𝑖𝑖
where A, B and C are  𝑥𝑥𝑖𝑖 𝑃𝑃𝑖𝑖 0 = 𝑦𝑦𝑖𝑖 𝑃𝑃𝑇𝑇
𝑇𝑇+𝐶𝐶𝑖𝑖
constants for each chemical species 𝑃𝑃𝑖𝑖 0
⇒ 𝑥𝑥𝑖𝑖 = 𝑦𝑦𝑖𝑖
𝑃𝑃𝑇𝑇
 Typical units for 𝑃𝑃𝑖𝑖 0 is mmHg (1 atm = 760
mmHg) and T is °C 𝑷𝑷𝒊𝒊 𝟎𝟎
⇒ Define distribution coefficient, 𝑲𝑲𝒊𝒊 =
𝑷𝑷𝑻𝑻

⇒ 𝒙𝒙𝒊𝒊 𝑲𝑲𝒊𝒊 = 𝒚𝒚𝒊𝒊

For n components: ⇒ 𝐾𝐾𝑖𝑖 is a function of 𝑃𝑃𝑇𝑇 and T for ideal systems
∑𝑛𝑛𝑖𝑖=1 𝑥𝑥𝑖𝑖 = ∑𝑛𝑛𝑖𝑖=1 𝑦𝑦𝑖𝑖 = 1
• 𝐾𝐾𝑖𝑖 for hydrocarbons can be obtained from
DePriester Chart

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 5

DePriester Chart
(High T, SI Units)

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 6

 DePriester Chart
(Low T, SI Units)

What are the K values of methane,

ethane and propane at -10°C and 1 atm?
VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 7
 Test Your Understanding
Example 1: Calculating Vapor Pressure
The Antoine equation constants for water are as follows (for the form and units given on Slide 5).
Calculate the vapor pressure of water at 100°C.
A B C Tmin (°C) Tmax (°C)
8.07131 1730.63 233.426 1 100

The vapor pressure is 760 mm Hg

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 8

 Test Your Understanding
Example 2: Binary Phase Diagrams
The binary equilibrium data for ethanol-water system at 1 atm is given below. The T-x-y and x-y plots
are given on the next slide.

𝒙𝒙𝑬𝑬 𝒙𝒙𝒘𝒘 𝒚𝒚𝑬𝑬 𝒚𝒚𝒘𝒘 𝑇𝑇, 𝑜𝑜 𝐶𝐶

0 1.0 0 1.0 100
0.019 0.981 0.17 0.83 95.5
0.0966 0.9034 0.4375 0.5625 86.7
0.1661 0.8339 0.5089 0.4911 84.1
0.2608 0.7382 0.5580 0.4420 82.3
0.3965 0.6035 0.6122 0.3878 80.7
0.5198 0.4802 0.6599 0.3401 79.7
0.6763 0.3237 0.7385 0.2615 78.74
0.7472 0.2528 0.7815 0.2185 78.41
1.0 0 1.0 0 78.3

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 9

a) Which component have the graphs been plotted for?
b) What is the composition of the vapor in equilibrium with
liquid of composition 0.2? What is the corresponding
temperature of the system?
c) 100 kmol/h of a subcooled liquid with composition 0.4 is
heated to 85°C. What are the liquid and vapor
compositions and flow rates?

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 10

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 11
 Binary Phase Diagrams
• Shown for ethanol-water system at 1 atm
• Can be derived experimentally or by calculations
• Top diagram is x-y plot, bottom diagram is T-x-y plot
• Ethanol has a higher vapor pressure and hence lower boiling
point than water => is the more volatile component
 𝑦𝑦𝐸𝐸 > 𝑥𝑥𝐸𝐸
• The red diagonal line on the x-y plot is an important line, and
has constructional significance in the graphical procedures
covered later
• How do you think the two plots can be derived by
calculation?

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 12

 A Closer Look
• Point P: Subcooled liquid with composition
0.4
• Point Q: First vapor bubbles appear =>
T
bubble point, liquid phase composition =
0.4, vapor phase composition = 0.62

S • Point R: Two-phase region, isotherm/tie

line gives liquid and vapor phase
Lever arm rule: compositions, liquid phase composition =
B 𝐿𝐿 𝐵𝐵𝐵𝐵
A R = 0.2, vapor phase composition = 0.53
𝑉𝑉 𝐴𝐴𝐴𝐴
Q • Point S: Last droplets of liquid => dew point,
P liquid phase composition = 0.08, vapor
phase composition = 0.4
• Point T: Superheated vapor with
composition 0.4

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 13

 Relative Volatility and Approximate Equilibrium Data
𝑲𝑲𝑨𝑨 𝑷𝑷𝑨𝑨 𝟎𝟎 • The x-y plot can be generated using the 𝛼𝛼𝐴𝐴𝐴𝐴
• 𝜶𝜶𝑨𝑨𝑨𝑨 = =
𝑲𝑲𝑩𝑩 𝑷𝑷𝑩𝑩 𝟎𝟎 equation:
• Though 𝑃𝑃𝐴𝐴 0 and 𝑃𝑃𝐵𝐵 0 are functions of  Inherent assumption that 𝛼𝛼𝐴𝐴𝐴𝐴 is constant
temperature, their ratio is not  𝜶𝜶𝑨𝑨𝑨𝑨 > 𝟏𝟏 since by convention A is lighter
• Rearranging the equation for 𝛼𝛼𝐴𝐴𝐴𝐴 gives another than B
relation between 𝑥𝑥𝐴𝐴 and 𝑦𝑦𝐴𝐴 : • Equilibrium data can be generated:
𝑦𝑦𝐴𝐴 𝑦𝑦𝐴𝐴  If 𝛼𝛼𝐴𝐴𝐴𝐴 is given
𝐾𝐾𝐴𝐴 �𝑥𝑥𝐴𝐴 �𝑥𝑥𝐴𝐴
𝛼𝛼𝐴𝐴𝐴𝐴 = = 𝑦𝑦𝐵𝐵 = (1−𝑦𝑦  If 𝑃𝑃𝐴𝐴 0 and 𝑃𝑃𝐵𝐵 0 or 𝐾𝐾𝐴𝐴 and 𝐾𝐾𝐵𝐵 are known
𝐾𝐾𝐵𝐵 �𝑥𝑥𝐵𝐵 𝐴𝐴 )
�(1−𝑥𝑥 )
𝐴𝐴

𝜶𝜶𝑨𝑨𝑨𝑨 𝒙𝒙𝑨𝑨
=> 𝒚𝒚𝑨𝑨 =
𝟏𝟏+ 𝜶𝜶𝑨𝑨𝑨𝑨 −𝟏𝟏 𝒙𝒙𝑨𝑨
• Larger value of 𝛼𝛼𝐴𝐴𝐴𝐴 means A is much lighter 𝑦𝑦𝐴𝐴
than B => easier to separate A and B
Increasing 𝛼𝛼𝐴𝐴𝐴𝐴

𝑥𝑥𝐴𝐴
VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 14
 Flash Distillation: The Simplest Separation Process
Prevents liquid droplets from
being entrained in vapor

Typical flash set-up • Fluid pressurized and

for a liquid feed heated, and passed
through a throttling valve
into the flash drum
• Part of the fluid
vaporizes due to the
large drop in pressure

• Part of liquid vaporizes or part of vapor condenses (how?) in a flash chamber

• The vapor and liquid in equilibrium with each other are separated => IMPORTANT
• More volatile component will be concentrated more in the vapor
• A large degree of separation is usually not achieved
• The first choice of separation technique in any process when there are components with a huge
difference in boiling points
• Very suitable technique for desalination
VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 15
 Flash Distillation: Industrial Example

Recycle
Compressor
Fresh Gas Recycle
Hydrogen

Furnace PFR
Fresh Outlet
Toluene
Total PFR
HX PFR Purge
Feed Toluene Inlet
Pump Purge Valve

Separator
Cooler
Recycle Toluene

Recycle Pump

Benzene Product Fuel Gas

Toluene Benzene
Column Stabilizer
Column

Diphenyl

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 16

 Key Process Data Stream Flow (lb T (°F) P Composition (mole fraction)
Stream Flow (lb T P Composition (mole mole/h) (psia)
mole/h) (°F) (psia) fraction)
Furnace inlet 4383 1106 513 M: 0.48, H: 0.43, T: 0.09
Fresh 291 86 575 T: 1 Reactor inlet 4383 1150 503 (some B)
toluene
Reactor effluent 4383 1263 486 M: 0.55, H: 0.36, B: 0.07, T:
Fresh 490 86 575 H: 0.97, M: 0.03
0.02
hydrogen
Quench 156 113 486 B: 0.72, T: 0.21, M: 0.05, D:
Purge gas 637 115 480 M: 0.59, H: 0.40 (Rest B/T)
0.02
Stabilizer gas 21 113 480 M: 0.93, B: 0.07
FEHE hot in 4539 1150 486 M: 0.53, H: 0.35, B: 0.09, T:
Benzene 273 211 30 B: 0.9997, T: 0.0003
FEHE hot out 4539 337 480 0.03
product
Separator gas 4156 113 486 M: 0.59, H: 0.40 (Rest B/T)
Diphenyl 6.8 559 31 D: 0.99974, T: 0.00026
out
product
Stabilizer feed 383 113 480 B: 0.72, T: 0.21, M: 0.05, D:
Gas recycle 3519 115 513 M: 0.59, H: 0.40
0.02
Toluene 82 272 30 T: 0.99937 (Rest B/D)
Stabilizer 361 200 480 B: 0.75, T: 0.23, D: 0.02
recycle
bottoms
H: Hydrogen, M: Methane, B: Benzene, T: Toluene, D: Diphenyl Product bottoms 89 283 33 T: 0.92, D: 0.08
VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 17
 Flash Distillation: Nomenclature and The Problem

Stream Nomenclature Simplified Nomenclature

Feed, F 𝑧𝑧𝐴𝐴 , 𝑧𝑧𝐵𝐵 𝑧𝑧 for more volatile component
Vapor, V 𝑦𝑦𝐴𝐴 , 𝑦𝑦𝐵𝐵 𝑦𝑦 for more volatile component
Liquid, L 𝑥𝑥𝐴𝐴 , 𝑥𝑥𝐵𝐵 𝑥𝑥 for more volatile component

• Given variables:

• V and L are in equilibrium  F, 𝑧𝑧𝐴𝐴 , 𝑧𝑧𝐵𝐵 , 𝑇𝑇1 , 𝑃𝑃1

𝒚𝒚𝒊𝒊 • Gibbs phase rule for a binary vapor-liquid system:

 𝑲𝑲𝒊𝒊 = (reliable equilibrium data)
𝒙𝒙𝒊𝒊  𝐷𝐷𝐷𝐷𝐷𝐷 = 𝐶𝐶 − 𝑃𝑃 + 2 = 2 − 2 + 2 = 2
 V and L are at Pdrum and Tdrum • 4 independent variables:
• 𝑥𝑥𝐴𝐴 + 𝑥𝑥𝐵𝐵 = 1  𝑥𝑥𝐴𝐴 , 𝑦𝑦𝐴𝐴 , 𝑇𝑇𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 , 𝑃𝑃𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑
• 𝑦𝑦𝐴𝐴 + 𝑦𝑦𝐵𝐵 = 1 • We can only fix 2 of the 4 independent variables

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 18

 • Mass balance:
 𝐹𝐹 = 𝐿𝐿 + 𝑉𝑉 (overall)
 𝐹𝐹𝐹𝐹 = 𝐿𝐿𝐿𝐿 + 𝑉𝑉𝑉𝑉 (more volatile component)
• Energy balance: • Component
mass balance is
 𝐹𝐹ℎ𝐹𝐹 + 𝑄𝑄 = 𝐿𝐿ℎ𝐿𝐿 + 𝑉𝑉𝐻𝐻𝑉𝑉 very important
• Equilibrium: in separation
process design.
 𝑦𝑦𝐴𝐴 = 𝐾𝐾𝐴𝐴 𝑥𝑥𝐴𝐴 • Streams leaving
 𝑦𝑦𝐵𝐵 = 𝐾𝐾𝐵𝐵 𝑥𝑥𝐵𝐵 a stage are in
equilibrium.
• Degrees of freedom:
• Given variables:
 Number of equations = 5
 F, 𝑧𝑧𝐴𝐴 , 𝑧𝑧𝐵𝐵 , 𝑇𝑇1 , 𝑃𝑃1 => 5
 Number of unknowns = 7
• Unknown variables:
 Degrees of freedom = 7 − 5 = 2
 L, x, V, 𝑦𝑦, 𝑃𝑃𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 , 𝑇𝑇𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑 , 𝑄𝑄 => 7
 One degree of freedom is usually 𝑃𝑃𝑑𝑑𝑑𝑑𝑑𝑑𝑑𝑑

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 19

 Test Your Understanding
Example 1: Degrees of Freedom
• Determine the system pressure that is required to bring a 50:50 liquid mixture of A:B to come to
equilibrium with its vapor mixture at 70oC. Is this possible?
1. Yes
2. No

• A binary vapor-liquid system is at 50oC and 1 atm pressure. Is it possible to find compositions of the
two phases?
1. Yes
2. No

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 20

 Class Exercise
Example 2: Excel DePriester Chart
• Let us first familiarize ourselves with the DePriester Chart in Excel developed by Prof Farooq.

• We will then use the excel file to calculate the bubble point of a mixture of propane and n-butane at
101.3 kPa when mole fraction of propane in the liquid mixture is 0.35.

• We will use the Solver function in Microsoft Excel.

VasudevanS/TCN3132/Basics of Equilibrium and Introduction to Flash Distillation 21