Muazzamuddin

Shah
CENGM011
Process Modelling
and Design CW 3
Tutor: Eric Fraga
Muazzamuddin Shah
Advanced Process Modelling and
Design CW3
Tutor:
Prof.E.Fraga

Muazzam

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

Absorption column separating CO

from a flue gas using a solution of
MEA

Contents
1. Summary........................................................................................................... 2
2. Mathematical Model equations with description................................................2
2.1. Physical properties and single-stage model................................................2
2.1.1 Liquid phase (bottom of column)............................................................2
2.1.2. Vapor Phase (top of column).................................................................3
2.2. Single Stage description.............................................................................. 4
2.2.1 Material balance..................................................................................... 4
2.2.2. Degrees of freedom............................................................................... 6

1. Summary

2. Mathematical Model equations with description

2.1. Physical properties and single-stage model
Using formulas available, a single equation expression has to be derived for the
liquid and vapor molar volumes in terms of mole fraction, pressure and
temperature. Molar volume (m3/kmol) is defined by the volume occupied per unit
kilo-mole can be calculated using the following equation:

Vm=

V
n

(1)

2.1.1 Liquid phase (bottom of column)

Below are the volume equations in terms of mass and molar density,
respectively:
L
j

V =

mLj
L
mass
,j

Key (used in whole

document):
i = stage in column
j = component
L = liquid
V = vapor

(2)

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Tutor: Eric Fraga

V Lj =

CENGM011 Process Modelling and Design CW 3

n Lj
nL, j

(3)

Therefore

m Lj

n Lj
=
Lmass, j Ln , j
(4)

m Lj
n=
MW j
L
j

As

(5)

Substitute equation (5) into equation (4) and rearrange to get:

L

= mass , j
MW j
L
n, j

(6)

Therefore
L

n MW j
V = jL
mass , j
L
j

; therefore

V Lm , j=

MW j
L
mass
,j

(7)
Equation 6 represents the relationship between molar density and mass density.
The liquid density is assumed to be constant as the heat of solution is so small
that the temperature can be assumed to be constant, also perfect mixing is
assumed. This equation is derived assuming that the densities are independent
of temperature and that there is perfect mixing.
2.1.2. Vapor Phase (top of column)
Assuming that the vapor present is an ideal gas i.e. constant temperature and
pressure, the ideal law equation (8) can be applied.

PVj V Vj =nVj RT

(8)

This is rearranged to:

V

V j RT
= V
V
nj
Pj

(9)

As vapor molar volume is derived by:

Muazzamuddin Shah
Tutor: Eric Fraga

V Vm , j=

CENGM011 Process Modelling and Design CW 3

V Vj
nVj

(10)
Now sub (9) into (10) to get:

V Vm , j=

RT
V
Pj

(11)

Raoults law states that the vapour pressure of a solution equals the
product of the vapour pressure of the pure solvent and the mole fraction
of solvent. Using this law we can calculate the total pressure and mole
fraction using the below equation:
V

y Vj =

Pj
V
PT
(12)

Rearranging equation (12) and making P Vj the subject, it can then be substituted
into equation (11) to form the below expression:

V Vm , j=

RT
PVT y Vj
(13)

2.2. Single Stage description

2.2.1 Material balance
Below figure 2.2.1.1 represents the material balance diagram for an equibrium
stage. This represents stage i of the equilibrium stage. A material balance is
going to be carried out on stage i.

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

Stage i material balance:

d mi , j
=out
dt
(14)

d mi , j
out
out out
=Li xi , j +V i y i , jLout
yi , j
i x i, j V i
dt

(15)

As it has been assumed that there is perfect mixing throughout the column, this
means stage i will also have perfect mixing. Using this fact, following can be
assumed and derived:
Assumptions:

x out
i , j =x i , j
(16)

y out
i , j = yi , j
(17)
When the assumptions (16) and (17) are substituted into equation (15), the
below, equation (18) is derived:

d mi , j
out
=Li xi , j +V i y i , jLout
i x i, j V i y i , j
dt

(18)

Mass balance on total holdup in stage i:

L

M i , j =M i x i , j+ M i y i , j
(19)
L

M M
V i= Lj + Vi
j j
(20)
Where

V i= Ai hi
(21)

Substitute equation (21) into equation (20):

Muazzamuddin Shah
Tutor: Eric Fraga

Ai hi=

CENGM011 Process Modelling and Design CW 3

M Lj M Vi
+
Lj Vj

(22)
The average densities of the liquid and vapor, with NC number of components
can be calculated respectively using equations below:
NC

= Lj x i , j
L
i

j=1

(23)
NC

i = j y i , j
V

j =1

(24)
Mole fractions are calculated as a fraction of the total number of moles.
Therefore the mole fractions of each component in each phase should total up to
equal 1.

NC
j 1

x j,i 1
(25)

NC
i1

y j,i 1
(26)

Henrys Law: At a constant temperature, the amount of a given gas dissolved in a

given type and volume of liquid is directly proportional to the partial pressure of
that gas in equilibrium with that liquid.
Using Henrys Law. The vapour mole fractions can be calculated:

y i , j=

k H , j xi , j
Pj
(27)

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

Vi (Pi Pi1)
(28)

L,in L,out
(29)
2.2.2. Degrees of freedom
Equation

V Lm , j=

MW j

Equat
ion
Numb
er
7

Unknown
Variables

Number
of
Variable
s
0

Number
of
Equation
s
NC

11

Pj

NC

12

y Vj

NC

NC

5NC + 4

NC

NC

L
mass
,j

V m , j=

RT
PVj

PVj
y = V
PT
V
j

18
d mi , j
out
=Li xi , j +V i y i , jLout
i x i, j V i y i , j
dt

in
M j ,i ,Lini, xin
j ,i ,Vi
in
j ,i

out
i

out

y ,L ,Vi ,

xi , j ,
yi , j ,
M i , j =M Li x i , j+ M Vi y i , j

22

iL j 1 Lj x j,i

23

NC

iv j 1 vj y j,i

24

Vj

NC

x j,i 1

25

y j,i 1

26

NC

NC

M iL M iv

M M
Ai hi= Lj + Vi
j j

19

NC

j 1
NC
i1

j , j

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

k H , j xi , j

27

NC

V i=(PiPi1 )

28

L,in L,out

29

8NC+9

6NC+7

y i , j=

V
j

Total

Table 1: degrees of freedom

Degrees of Freedom = (number of variables) (number of equations)
(30)
= (8NC+9) (6NC+7)
= 2NC + 2

Specification

x inj,i

Number of Known Variables

NC

y inj,i

NC

Lini

Viin

Total

2NC +2
Table 2: Single Stage

DOF = (2NC+2)-(2NC+2)
=0

After the above specifications have been specified, the degrees of freedom is
now zero and the above model can now be solved as enough variables have
been specified.

2.3. Stage-section model

Now the whole of the absorption column is to be modeled, taking into
consideration of every stage present. Below is a diagram of the column which
has Ns number of stages:

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

The above column in figure 2.3.1, which is being considered is a six stage packed
absorption column, i.e. Ns = 6.
2.3.1. Material Balance
The above equations which are in terms of i (the number of stages), now have to
be included and related to the degrees of freedom analysis in the single stage
model. The inlet molar flowrate and fractions require specification of the single
stage ith stage. The outlet of a previous stage is the inlet of the next stage, for
instance flow out of stage 1 is equal to flow into stage 2. This is modelled below:
out
Viin Vi1

; for j=1, , Ns

(31)

Lini Lout
i1

; for i=2,, Ns
(32)

x inj,i x out
j,i1
; for j, i=2,, Ns
(33)

y inj,i y out
j,i1
; for

j, i=1, , Ns

(34)

Stage 1:

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

Initially the liquid molar flow-rate is pure MEA into the absorption column,
therefore the liquid flowing into stage one is
of component j in stage one us

x j ,1

L1 ( L1=L ) and the the fraction

( x j ,1 = x j )

Similarly, the inlet vapour molar flow rate and mole fraction to the final stage
(j=Ns) are the vapour feed specification:

VNsin V in

(30)

in
y i,Ns
y iin

(31)

The vapour output of stage 1 corresponds to the purified product stream, while
the final out put represents a purified liquid amine product:

out
Lout
Ns L

(32)

out
x out
j,Ns x j

(33)

V1out V out

(34)

out
y out
j,1 y j

(35)

1.3.2 Degrees of Freedom Analysis on Stage Section Model

10

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

Previously we have concluded that there are 2NC+4 degrees of freedom without
the specification being involved. Since there are N s stages to be considered
therefore there are now Ns(2NC+4) degrees of freedom. But the above equation
(23) to (35) equations, which looks at column specifications (L in , Vin, xjin, yjin), the
number of degrees of freedom reduces to 2Ns. This is shown in table 3 below.

Table 3: Single Stage Specification

Specification

Number of Known Variables

1

Viin

x inj

NC

y inj

NC

Total Number of Specification

2NC +2

in
i

Equation 21 and 22, which were previously written single stage will be expanded
here further:

The vapour flow rate between each stage is given by the tray hydraulics from
each stage:

v j (P j P j 1)
j= 2, , Ns

v j (Pj Pout )
j= 1

Therefore one of Ns equation is resolved. We now need another one.

Since the rate of absorption is small in can be concluded that the inlet follow rate
is equal to the outlet liquid flow rate:

11

Muazzamuddin Shah
Tutor: Eric Fraga

CENGM011 Process Modelling and Design CW 3

L j L j 1
j= 2, , Ns

Lj = Lin

j=1

Hence the 2Ns equations are now solved from equation 21 and 22, which were
previously used but were expanded to be able to use as N s trays.

Consequently we now have zero degrees of freedom, for N s number of trays.

12