Isothermal Flash Configuration

Consider the following operation which produces a liquid-vapor equilibrium from a

liquid feed:

Flash Drum

Liquid Feed Vapor out

V, yi, TV, PV, hv
F, zi, TF, PF, hF
Q Liquid out
L, xi, TL, PL, hL

For each stream:

n: molar flow rate: F, L, V
zi: composition variables: x,y,z
T: temperature
P: pressure
h: enthalpy
Q: heat transfer

1
 Isothermal Flash Variables
Flash Drum
Liquid Feed Vapor out
V, yi, TV, PV, hv
F, zi, TF, PF, hF
Q Liquid out
L, xi, TL, PL, hL

For this system there are 3C+10 variables: F, V, L, TF, PF, TV, PV, TL, PL, Q, {xi , yi ,zi}C

For single-stage equilibrium, there are C+5 degrees of freedom

Assuming that C+3 feed variables F, TF, PF and C values of zi are known,
two additional variables can be specified.

Common Specifications:
TV,PV Isothermal Flash
V/F=0, PL Bubble-Point Temperature
V/F=1, PV Dew-Point Temperature
V/F=0, TL Bubble-Point Pressure
V/F=1, TV Dew-Point Pressure
Q=0, PV Adiabatic Flash
Q, PV Non adiabatic flash
V/F, PV Percent Vaporization Flash
2
 Isothermal Flash Equations
If we specify TV (or TL) and PV (or PL) of a multicomponent mixture

Then remaining 2C 5 variables must be found from the same number of equations:

1) Mechanical equilibrium PV = P L 1

2) Thermal equilibrium TV = TL 1

3) Phase equilibrium Ki = yi /xi C

Note that if T and P of each
4) Component mole balance Fzi = V yi + L xi C-1 product stream are not
considered as variables, then
we wouldn’t have equations
5) Total mole balance F=V+L 1 for thermal and mechanical
equilibrium in the drum.
6) Energy balance hf F+Q = hv V+hL L 1

7) Summations 𝑥𝑖 = 1 1
𝑦𝑖 = 1 1
Total Eqs = 2C + 5

If less than C+5 variables are specified, then the system is undetermined (underspecified).
If more than C+5 variables are specified, then the system is over-determined (over-specified).
3
 Rachford Rice Derivation

It is convenient to define the Vapor Fraction as follows:

V
F
Substituting into our total material balance:

L F F
For the component material balances:

FZi VYi LXi Zi VYi F F Xi Zi Yi Xi Xi

F F
Using the K-Value and solving for the liquid phase mole fraction:

Zi Yi Xi Xi Zi Ki Xi Xi Xi Zi
Xi
Ki 1
Yi KiXi
We use the K-Value to get:

Yi KiZi
Ki 1
4
 Rachford Rice Equations

We use the mole fraction summations:

i
Xi 1
i
Yi 1 Xi Yi 0
i
Substituting in our expressions for the mole fractions:

Xi Zi KiZi
Ki 1 Yi
Ki 1
Gives us the Rachford-Rice Equation:

Zi KiZi f( ) Zi 1 Ki 0
0
i Ki 1 Ki 1 i Ki 1
The roots of this equation give us the compositions, and vapor fraction of the
Isothermal Flash operation.

5
 Newton’s Iterative Method

To solve the Rachford-Rice equation we can use Newton’s method to find :

Newton’s method estimates a better f k

root using the last guess and the ratio k1 k
of the function to its derivative at that f' k
guess:

Zi Ki 1
kK 1 1
For the Rachford-Rice Equation k1 k i i
this becomes:
Zi Ki 1 2
2
i k Ki 1 1

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 Rachford-Rice Procedure

The Rachford-Rice procedure using Newton’s method is then:

Step 1: TL TV Thermal equilibrium

Step 2: PL PV Mechanical equilibrium

Step 3: Solve Rachford-Rice for V/F where the K-values are determined by
TL, and PL.
Zi 1 Ki 0 Can use Newton’s method here.
i Ki 1
Step 4: V F Determine V

Xi Zi KiZi
Steps 5 and 6: Yi
Ki 1 Ki 1
Step 7: L F F Determine L

Step 8: Q Vhv Lhl Fhf Determine Q

7
 Problem
A 100 kmol/h feed consisting of 10,20,30,40 mol% of propane(3), n-butane(4), n-pentane(5),
and n-hexane(6), respectively, enters a distillation column at 100 psia (689.5 kPa) and 200 oF
(366.5 K). Assuming equilibrium, what fraction of the feed enters as liquid and what are the
liquid and vapor compositions?
 Problem

Flash adiabatically, across a valve, a stream composed of the six hydrocarbons

given below. The given temperature and pressure are 250 oF and 500 Psia.
Determine the mole fraction compositions of vapor and liquid phases.

Component zi
Ethene 0.02
Ethane 0.03
Propene 0.05
Propane 0.1
Iso-butane 0.2
n-butane 0.6
 Azeotropic Systems
Minimum boiling point azeotrope: Isopropyl ether-Isopropyl alcohol system Negative deviation

Tetrahydrofuran/CCl4 at 30 oC.

Chloroform/Tetrahydrofuran
at 30 oC

Forces between unlike molecules > like molecules

 Azeotropic Systems
Maximum boiling point azeotrope: Acetone- Choloroform system Positive deviation

Furan/CCl4 at 30 oC.

Ethanol/Toluene at 65 oC.

Forces between like molecules > unlike molecules

 Problem
For the system methanol (1)/methyl acetate (2), the following equations provide a
reasonable correlation for the activity coefficients:

ln 1 (2.771 0.00523
T)x22 ln 2 (2.771 0.00523
T)x12
The Antoine equations provide vapor pressures:

lnP1sat/ kPa 16.59158 3643.31 lnP2sat/ kPa 14.25326 2665.54

T(K) 33.424 T(K) 53.424

Calculate the azeotropic pressure and the azeotropic composition for T = 318.15
K?
 Solution
- First determine whether or not an azeotrope exists at the given temperature
- This calculations is facilitated by the definition of a quantity called the relative
volatility:
y1 / x1 At an azeotrope: y = x , y = x
12 12 = 1.
y2 / x2 1 1 2 2

sat P
In general,
yi i Pi 12
1 1
sat

xi P P
2 2
sat

@ x1 = 0, 1 = eA and 2 = 1;
Since, 1 eAx 2 e
Ax
2 2
2 1

@ x1 =1, 1 = 1 and 2 = eA.

sat A
Therefore, in these limits, ( ) P1 e P sat
sat ( 12)x 1 PsateA
1
12 x 0
sat
1
P2 2
1

@ T = 318.15 K: P1 44.51 P2 65.64kPa A = 1.107

sat

( 12)x (44.51)e1.107 2.052 ( 12)x 1 44.51 0.224

0
1
65.54 1
(65.64)e1.107
Since the value at one limit is greater than 1, whereas the value at the other limit is less than
1, an azeotrope exists, because 12 is a continuous function of x1 and must pass through the
value of 1.0 at some intermediate composition.
 sat
Since, for the azeotrope =1
1P1 1
12 sat
1P1
12
az sat
or
1 P2 65.64 1.4747
az
2 P1sat 44.54
Since, ln 1 Ax22 & ln 2 Ax12
ln 1 Ax22 Ax22 A[(x1 1)2 x12] A(1 2x1)
2
ln(1.4747 ) 1.107(1 2x1az) x1az 0.325
Since at the azeotropic point, x1az y1az
Modified Raoult’s for species 1 becomes,
Paz 1azP1sat (1.657)(44.51) 73.76kPa
 Problem
For the system ethyl ethanoate (1) /n-heptane at 343.15 K,
show whether or not the system exhibits an azeotrope.
If there is then what is the composition and pressure?

P1sat = 79.8 kPa , P2sat = 40.50 kPa, A= 0.95

Use simple one parametric Marguels equation for the

activity coefficients calculation.
How to obtain equilibrium curve from phase diagram
 Relative Volatility

Recall
𝒚𝑨
𝑲𝑨 𝑷𝒔𝒂𝒕
𝑨 𝒙𝑨
𝜶𝑨𝑩 = = 𝒔𝒂𝒕 = 𝒚
𝑲𝑩 𝑷𝑩 𝑩
𝒙𝑩

𝒚𝑨 (𝟏 − 𝒙𝑨 )
𝜶𝑨𝑩 =
𝒙𝑨 (𝟏 − 𝒚𝑨 )

𝜶𝑨𝑩 𝒙𝑨
𝒚𝑨 =
𝟏 + 𝒙𝑨 (𝜶𝑨𝑩 − 𝟏)

𝜶𝑨𝑩 = 1 (no separation)

Azeotrope conditions

𝜶𝑨𝑩 > 1.2 for distillation to be economical 1) Yi = Xi

(Rule of thumb) 2) Ki = 1
 q-Line Concept
How to get xi and yi from xy diagram at given feed composition?

xH = 0.37, yH = 0.76
 q-Line Concept
How to get q-line?
Component mole balance, component 1

F z1 = V y1 + L x1
Total mole balance

F=V+L

Eliminate L and solve for y1

𝑳=𝑭−𝑽
𝑭𝒛𝟏 = 𝑽𝒚𝟏 + (𝑭 − 𝑽)𝒙𝟏

𝑽𝒚𝟏 = 𝑭𝒛𝟏 − (𝑭 − 𝑽)𝒙𝟏

𝟏
𝒚𝟏 = 𝒙 𝑽 − 𝑭 + 𝑭𝒛𝟏
𝑽 𝟏

𝑽−𝑭 𝑭
𝒚𝟏 = 𝒙𝟏 + 𝒛𝟏
𝑽 𝑽
 q-Line Concept

𝟏
(𝑽 − 𝑭)
𝒚𝟏 = 𝒙𝟏 𝑭 + 𝟏 𝒛
𝟏 𝑽 𝟏
𝑽 𝑭
𝑭

𝑽
−𝟏 𝟏
𝒚𝟏 = 𝒙𝟏 𝑭 + 𝒛
𝑽 𝑽 𝟏
𝑭 𝑭

φ = Vaporization of feed = V/F

𝝋−𝟏 𝟏
𝒚𝟏 = 𝒙𝟏 + 𝒛𝟏 q-line
𝝋 𝝋

𝝋−𝟏
Slope of q-line =
𝝋

If we know z1, V and F » can get q-line.

 Another Perspective on Relative Volatility

Raoult’s law applies

𝑷 = 𝒙𝑨 𝑷𝑨 + 𝒙𝑩 𝑷𝑩

𝑷 = 𝒙𝑨 𝑷𝑨 +(𝟏 − 𝒙𝑨 )𝑷𝑩

𝑷 = 𝑷𝑩 +𝒙𝑨 (𝑷𝑨 − 𝑷𝑩 )