Exercise 2: PRE

Delivered to Prof. Giuseppe Storti

By Mohamad Abou Daher
Equations
 
Instantaneous moments:

 Instantaneous degree of Polymerization and polydispersity

Equations
 
Instantaneous number and weight CLD

 
Such that
Equations
   account for mass transfer limitations on rate constants the following set of equations
To
were proposed:

Set of differential equations

Equations
  Conditions
Initial

Cumulative values
Methodology

To  determine the exact values of at required conversion the analytical solution for M and
was written such that and and required time for conversion (t) was solved. While solving
the equation were assigned as global variables enabling executing their values.

 For the cumulative DP and Pd the the PDE above was solved for 3e4 s until complete
conversion.
 Based on results analysis the configuration was modified to a CSTR to reach X=0.35
followed by a PFR
Case Studies

 Accounting for mass transfer limitations

1. Dominant termination by disproportionation (Cfm = 0, Ct = 1000)
2. Dominant termination by combination (Cfm = 0, Ct = 0.001)
3. Dominant chain transfer to monomer and negligible termination by combination (C fm =
0.01, Ct = 1000)
 Assuming constant kinetic constants for all 3 cases above

 Mass transfer limitations considering first case but with kp=75

 1st case number and weight distribution
fn instanteneous fw instanteneous
0.4 0.6

0.35
0.5

0.3 0.1
0.4
0.7 0.4
0.25 0.9
0.1
0.4
0.2 0.3
0.7
0.9
0.15
0.2

0.1

0.1
0.05

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
 1st case DPn, DPw, Pd

104
14 1.99999950099875
Pdi ns
1.9999995009987
12
1.99999950099865

10 1.9999995009986

1.99999950099855
8
1.9999995009985
6
1.99999950099845

4 1.9999995009984
DPn i ns
DPw i ns 1.99999950099835
2
1.9999995009983

0 1.99999950099825
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 2nd case number and weight distribution

fn instanteneous
0.6 fw instanteneous
0.7

0.5 0.6

0.5
0.4

0.4
0.3

0.1 0.3
0.4 0.1
0.2 0.7 0.4
0.9 0.2 0.7
0.9
0.1
0.1

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
 2nd case DPn, DPw, Pd

105
2.5 1.5009985019977
Pdi ns
1.50099850199765
2
1.5009985019976

1.50099850199755
1.5

1.5009985019975

1
1.50099850199745
DPn i ns
DPw i ns
1.5009985019974
0.5
1.50099850199735

0 1.5009985019973
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 3rd case number and weight distribution

fn instanteneous
0.4 fw instanteneous
0.1 0.6
0.4 0.1
0.35
0.7 0.4
0.9 0.5 0.7
0.3 0.9

0.25 0.4

0.2
0.3

0.15

0.2
0.1

0.05 0.1

0
0 1 2 3 4 5 6 0
0 1 2 3 4 5 6
 3rd Case DPn, DPw, Pd

2
200 Pd i ns

1.99999999995

180
1.9999999999

160 1.99999999985

1.9999999998
140
DPn i ns
DPw i ns 1.99999999975

120
1.9999999997

100 1.99999999965

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Analysis of 1st set
 Dp for the 1st and 2nd case increase as the system becomes more viscous leading to
autocatalysis of the reaction, then it decreases slightly with the depletion of the monomer.
 DP for 1st case encounters a slight increase with conversion due to the autocatalytic
behavior, but it is still almost constant at a level for Dpn= kp/kfm.
 As predicted DP order is : 2nd >1st >3rd
 The fn is broader than fw as expected and they shift in a manner similar to that of Dp. Thus
it’s expected to be overlapping and narrower in the case of dominant chain transfer.
 4th case number and weight distribution

fn instanteneous fw instanteneous
0.4 0.6
0.1 0.1
0.4 0.4
0.35
0.7 0.5 0.7
0.9 0.9
0.3

0.4
0.25

0.2 0.3

0.15
0.2

0.1

0.1
0.05

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
 4th Case DPn, DPw, Pd

11000 1.99999950099875
Pdi ns
10000 1.9999995009987

1.99999950099865
9000
DPn i ns 1.9999995009986
8000 DPw i ns
1.99999950099855
7000
1.9999995009985
6000
1.99999950099845
5000
1.9999995009984

4000
1.99999950099835

3000 1.9999995009983

2000 1.99999950099825
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 5th case number and weight distribution

fn instanteneous fw instanteneous
0.6 0.7
0.1 0.1
0.4 0.4
0.7 0.6 0.7
0.5
0.9 0.9

0.5
0.4

0.4
0.3
0.3

0.2
0.2

0.1
0.1

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
 5th case DPn, DPw, Pd

104
1.6 1.5009985019977
Pdi ns
1.50099850199765
1.4

1.5009985019976
DPn i ns
1.2 DPw i ns
1.50099850199755

1 1.5009985019975

1.50099850199745
0.8

1.5009985019974

0.6
1.50099850199735

0.4 1.5009985019973
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 6th case number and weight distribution

fn instanteneous fw instanteneous
0.4 0.6
0.1 0.1
0.4 0.4
0.35
0.7 0.5 0.7
0.9 0.9
0.3

0.4
0.25

0.2 0.3

0.15
0.2

0.1

0.1
0.05

0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
 6th case DPn, DPw, Pd

200 1.99999999985
Pdi ns
1.9999999998
180
DPn i ns
1.99999999975
DPw i ns
160
1.9999999997

140 1.99999999965

1.9999999996
120

1.99999999955

100
1.9999999995

80 1.99999999945
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Analysis of 2nd set
 Ignoring Mass transfer limitations on kinetic constants leads to underestimation of DP
except for the 3rd case where almost flat plots where obtained with close values to previous
ones.
 The drop in DP could BE attributed to ignoring of the contribution of autocatalytic
behavior of the system leading to main increase in DP as result of drop in α,β and γ with
conversion.
 Consequently the mean of fn and fw would be shifted to the left, but they’ll still follow the
pattern of DP.
 7th case number and weight distribution
fn instanteneous
0.4
fw instanteneous
0.1 0.6
0.4
0.35 0.1
0.7
0.4
0.9
0.5 0.7
0.3 0.9

0.25
0.4

0.2
0.3
0.15

0.1 0.2

0.05
0.1

0
0 1 2 3 4 5 6
0
0 1 2 3 4 5 6
 7th case DPn, DPw, Pd

104
6
1.99999950099875
Pdi ns
5 1.9999995009987

1.99999950099865
4
DPn i ns 1.9999995009986
DPw i ns
1.99999950099855
3
1.9999995009985

2 1.99999950099845

1.9999995009984
1
1.99999950099835

1.9999995009983
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
1.99999950099825
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
7th case conversion vs time
Conversion vs Time
1

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
0 0.5 1 1.5 2 2.5 3
4
10
 7th case cumulative DPn, DPw, Pd

Cummualtive DP values vs Time

6000
Pd vs Time

50

5000

40

4000
30
DP, -

3000
20

-
2000 DPn
10
DPw

1000 0

0 -10 Pd
0 0.5 1 1.5 2 2.5 3
0 0.5 1 1.5 2 2.5 3
Time, s 104 Time, s 104
Analysis of 3rd set

 Decreasing the value of kpo by 10 folds led to a drop in DP values by almost the half. This
is due to the increase in αand γ
 However DP doesn’t reach a maximum then decrease this could be attributed to the
increased contribution of glass effect on the effective kp value. And as more time is
required in converting the monomer R would decrease as I2 is being depleted leading to
lower α and γ .
 The fn and fw follow a similar pattern as DP and still maintain similar mean values as in 1 st
case since the ratio of α and γ are similar.
 The required conversion time is very high due to slow kinetics even though in industrial
application operating at very high conversions is avoided due to the glass effect.
Analysis of 3rd set
 Cumulative DP values increase with the increase in instantaneous DP as well as increase in
Polymer Productivity until conversion reaches a plateu leading to drop in cumulative DP
value.
 Cumulative Pd would express a bump with the increase in conversion due to the fast
increase and then decrease in cumulative values of DPw and DPn with varying ratio.
 Fn and fw cumulative values weren’t reported due to technical limitations in my laptop it
requires n+2 PDE and n is 10^6.
Optimization

 Even though this exercise was proposed to a batch reactor, considering the analogy
between batch reactors and PFR in terms of PDE the conversion is very slow at the
beginning taking into account the low radical concentration due to high termination rate.
 The conversion reaches high conversion rate after around 35% conversion. Thus it is
proposed to operate first in a CSTR until we reach X=0.35 then operate in a PFR to
complete the conversion.
 Instantaneous values and cumulative values are the same in CSTR assuming homogeneous
mixing and its output would act as the initial conditions for the PFR step.
Equations
  CSTR equations

 
 Optimized CSTR then PFR

Conversion vs Time
1

0.9

0.8

0.7

0.6

0.5

0.4

0.3
0.4 0.6 0.8 1 1.2 1.4 1.6
104
 Optimized PFR then CSTR

Pd vs Time Cummualtive DP values vs Time

2.8 9000

2.7
8000

2.6
7000
2.5

2.4 6000

DP, -
-

2.3 5000

2.2
4000
2.1

3000
2 DPn
Pd DPw
1.9 2000
0.4 0.6 0.8 1 1.2 1.4 1.6 0.4 0.6 0.8 1 1.2 1.4 1.6
4
Time, s 10 Time, s 104
Optimized PFR then CSTR

0.03
PFR
Optimized
0.028

0.026

0.024
I [mol/l]

0.022

0.02

0.018

0.016
0 0.5 1 1.5 2 2.5 3
time, s 4
10
Analysis of Optimized results
 Full conversion is obtained in almost half the time, however it expressed a different
behavior to that shown in a PFR system alone this could be due to the difference in inlet
conditions.
 The inlet value of cumulative DP and Pd are corresponding to those exiting the CSTR. The
different behavior expressed by DP and Pd could be attributed to the change in the
productivity rate.
 More over the initiator entering condition is much lower than the PFR case leading to
lower radical chains produced.
Thank You