Modeling of

Reactive Distillation
Modeling of
Reactive Distillation
John Schell
Dr. R. Bruce Eldridge
Dr. Thomas F. Edgar
Outline Outline
Overview of Reactive
Distillation

Project Overview
Tower Design
Steady-State Models
Dynamic Models and
Control
Individual Work
Column Design and
Operation
Validation of Models
Preliminary Dynamics
and Control Studies

Future Work
Reactive Distillation Reactive Distillation
Homogeneous or
Heterogeneous/
Catalytic Distillation
First Patents in 1920s
Applied in 1980s to
Methyl Acetate
Common applications:
Ethylene Glycol
MTBE, TAME, TAA

Favorable Applications
Westerterp (1992)
Match between reaction and distillation
temperatures
Difference in relative volatility between
product and one reactant
Fast reaction not requiring a large amount
of catalyst
Others: liquid phase reaction, azeotrope
considerations,exothermic reactions
Subawalla Approach (Dissertation)
1. Decide on a Pre-reactor
- Rate of reaction
- >1/2 of initial reaction rate at
80% of equilibrium
conversion
2. Pressure
3. Location of Zone
4. Estimate Catalyst
- Isothermal Plug-flow reactor
with ideal separators

5. Design Tower
- Size reaction zone
Catalyst requirements
Column diameter
- Determine reactant feed
ratio
- Feed location
- Reflux ratio
High reflux rate - 2-3
times non-rxtive column
- Diameter
Through-put
Catalyst density

Project Overview
Design and Construct TAME Column
Validate Steady State Models
Develop Dynamic Models
Test Control Algorithms
TAME Chemistry TAME Chemistry
Exothermic
Equilibrium Limited
45-62% at 50-80 C
Azeotropes
Catalyst: Amberlyst-15
Methanol can inhibit rates.
Rihko and Krause (1995)
MeOHS
a
MeOH+ S
a
TAMES
a

KB1
KB 2
MeOHS
a
+ 2M1B
TAMES
a

KB3
KB 4
MeOHS
a
+ 2M2B
TAMES
a
TAME+ S
a
2M2B
KB5
KB6
2M1B
S
a
is a vac ant adsorption site.
Pilot Plant (SRP)
Pilot Plant (SRP)
0.152-meter diameter
column
Finite reflux
7 meters of packing in 3
sections
Fisher DeltaV Control
Kochs Katamax

packing
Makeup MeOH
C5 from Cat
Cracker
Pre-Reactor
Reactive
Distillation
Column
Mixing
Tank
Back - Cracking
Reactor
Recycle
TAME
Unreacted C5,
MeOH
3.7
atm
SRP Pilot Plant
SRP Pilot Plant
Koch Spool
section, Katamax,
Catalyst
SRP - $145K


Steady-State Multiplicity Steady-State Multiplicity
Bravo et al. (1993)
Observed multiple steady-states in TAME CD
Hauan et al. (1997)
dynamic simulation provided evidence in MTBE
system
Nijuis et al. (1993)
found multiplicity in MTBE system
Jacobs and Krishna (1993)
found multiplicity in MTBE system
Steady-State Distillation Models Steady-State Distillation Models
Trayed Tower:
Equilibrium
Model


Rate Model
Packed Tower:
Continuous
Model
i i
j i j i j j i j
j i j j i j
Kx y
R y V x L
y V x L
=
+ +
= +
+ +
, , ,
1 , 1 1 , 1
L
i
V
i
N N =
( )

+ =
c
c
k
k L i
L
i i
R A AN L x
z
| u
TAME Reaction Rates
TAME Reaction Rates
Comparison of Reaction Rates
-0.06
-0.05
-0.04
-0.03
-0.02
-0.01
0
0.01
0.02
0.03
0.04
0.05
1 2 3 4 5 6 7 8 9
1
0
1
1
1
2
1
3
1
4
1
5
Stage (Condenser=1)
R
e
a
c
t
i
o
n

R
a
t
e
s

(
l
b
m
o
l
/
h
r
)
RADFRAC
RateFRAC
TAME Concentration Profile TAME Concentration Profile
Comparison of TAME Profiles
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1 2 3 4 5 6 7 8 9
1
0
1
1
1
2
1
3
1
4
1
5
Stage (Condenser=1)
M
o
l
e

F
r
a
c
t
i
o
n
RADFRAC
RateFRAC
Effective Reaction Rate
Effective Reaction Rate
Traditionally
simulations use
intrinsic reaction rate.
Effective rate is a
function of intrinsic
rate and diffusion
limitations.
Molefraction
E
f
f
e
c
t
i
v
e

R
a
t
e

Control for TAME Tower
Control for TAME Tower
Fisher DeltaV
Visual Basic
Matlab, Visual Studio

State Estimation
Temperature Profiles
Online Analyzers
Control Algorithms
PID
Linear MPC
Non-Linear MPC
Individual Work

Design and Construct RD Column for
Novel System
Steady State Model Validation
Dynamic Models and Control Study
Novel System
Kinetic Reaction
Not Equilibrium limited
Equilibrium Isomers
Exothermic
Kinetics from CSTR
Experiments
Feed is dominated by
inerts
Replace hazardous
heterogeneous catalyst



A + B C
1
C
1
C
3
C
2
Isomer Distribution for Reactive Systems
0
5
10
15
20
25
30
35
40
45
50
1 2 3 4 5
Isomer
M
o
l
e

%
Plug-flow Reactor
CD Column
Novel System Data
Novel System Data
Standard Conditions at 50 psig Over 26 Experiments
Overhead
Vapor
Temp
DA-220-1 DA-220-2 DA-220-3 DA-220-4 TI-215 DA-210-1 DA-210-2 DA-210-3 DA-210-4 Reboiler
Temp
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
5
10
15
20
25
High
Low
Average
Standard Deviation
Reactive Zone
Novel System Data
Novel System Data
Profiles for 35 psig at Standard Conditions
Overhead
Vapor Temp
DA-220-1 DA-220-2 DA-220-3 DA-220-4 TI-215 DA-210-1 DA-210-2 DA-210-3 DA-210-4 Reboiler
Temp
T
e
m
p
e
r
a
t
u
r
e

(
C
)
0
5
10
15
20
25
Hi
Lo
Average
Stnd Dev
Reactive Zone
Simulation Validation - 50 psig
Simulation Validation - 50 psig
Column Data and Simulation for Standard Flows at 50 psig
0 5 10 15 20 25
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Simulation Validation 35 psi
Simulation and Data for Standard Flows at 35 psig
0 5 10 15 20 25
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Effect of Pressure
Effect of Varying Pressure
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
T
e
m
p
e
r
a
t
u
r
e

(
C
)
25 psig
35 psig
50 psig
75 psig
Effect of Varying Feed Rate
Effect of Varying Reactant Feed Rates
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
T
e
m
p
e
r
a
t
u
r
e

(
C
)
25 g/min A and 10 g/min B
75 g/min A and 10 g/min B
100 g/min A and 10 g/min B
150 g/min A and 20 g/min B
Dynamic Modeling and Control
Study
Aspen Custom
Modeler/ Aspen
Dynamics
Validate Steady State
Solution
Validate Dynamic
Studies


Develop Control
Algorithms
PID
Linear MPC
NLMPC
Aspen Custom Modeler
Aspen Custom Modeler
Formerly Speed-Up
and DynaPlus
Equation Solver
Aspen Properties
Plus
Tear Variables
automatically
selected
Solves Steady-State
and Dynamic
Dynamic Events and
Task Automation

1 2 3 4 5 6 7 8 9 10
1 X X
2 X X
3 X X T T
4 X X T T
5 X X T T
6 X X T T
7 T T T T T T
8 T T T T T T
9 X
10 X
Equations vs. Variables
Validation of Dynamic Simulator
Validation of Dynamic Simulator
Comparison of ACM and Aspen Plus Radfrac Results
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23
T
e
m
p
e
r
a
t
u
r
e

(
C
)
ACM w/Tear
Aspen Plus
Feed Disturbance With Manual Control Feed Disturbance With Manual Control
Stream Results
Ti me Hours
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3
P
r
e
s
s
u
r
e

N
/
m
2
T
e
m
p
e
r
a
t
u
r
e

K
M
o
l
a
r

F
l
o
w

r
a
t
e

k
m
o
l
/
s
3
5
0
0
0
0
3
6
0
0
0
0
5
2
0
5
4
0
5
6
0
2
e
-
5
2
.
5
e
-
5
3
e
-
5
3
.
5
e
-
5
C - Production
Time Hours
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
B
-
F
e
e
d

R
a
t
e
B
-
P
r
o
d
u
c
t
C
1
.
5
e
-
5
2
e
-
5
2
.
5
e
-
5
3
e
-
5
-
0
.
0
5
0
0
.
0
5
0
.
1
0
.
1
5
0
.
2
Control of Reactive Distillation Control of Reactive Distillation
Configurations
DB
LV
BV, LB
Goals
Conversion
Product Purity
F
R
D
B
V L
Duty
Control of Reactive Distillation
Control of Reactive Distillation
Bartlett and
Wahnschafft (1997)
Simple Feed-Forward/
Feed-Back PI Scheme
Sneesby et al. (1999)
Two point control with
linear conversion
estimator
Kumar and Daoutidis
(1999)
Showed linear
controllers unstable for
ethylene glycol
systems
Demonstrated possible
Nonlinear MPC
scheme
Dependency of Conversion on
Reboiler Duty and Reflux Ratio
Dependency of Conversion on
Reboiler Duty and Reflux Ratio
Conversion vs Reboiler Duty
Conversion vs Reboiler Duty
Single Tray Conversion
Estimation
Dependency of Conversion on Temperature
0
50
100
150
200
250
300
350
400
0
.
0
0
0
.
1
0
0
.
2
0
0
.
3
0
0
.
4
0
0
.
5
0
0
.
6
0
0
.
7
0
0
.
8
0
0
.
9
0
1
.
0
0
Conversion
T
e
m
p
e
r
a
t
u
r
e

(
C
)
T8
T6
Single Tray Conversion
Estimation
Single Tray Purity Estimation
Purity of Alkylate
230
235
240
245
250
255
260
265
0
.
0
0
0
0
0
E
+
0
0
5
.
0
0
0
0
0
E
-
0
8
1
.
0
0
0
0
0
E
-
0
7
1
.
5
0
0
0
0
E
-
0
7
2
.
0
0
0
0
0
E
-
0
7
2
.
5
0
0
0
0
E
-
0
7
3
.
0
0
0
0
0
E
-
0
7
3
.
5
0
0
0
0
E
-
0
7
4
.
0
0
0
0
0
E
-
0
7
4
.
5
0
0
0
0
E
-
0
7
5
.
0
0
0
0
0
E
-
0
7
Benzene Concentration
T
e
m
p
e
r
a
t
u
r
e

(
C
)
T6
T7
T8
Single Tray Purity Estimation
Feed Disturbance With Manual Control Feed Disturbance With Manual Control
Stream Results
Ti me Hours
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3
P
r
e
s
s
u
r
e

N
/
m
2
T
e
m
p
e
r
a
t
u
r
e

K
M
o
l
a
r

F
l
o
w

r
a
t
e

k
m
o
l
/
s
3
5
0
0
0
0
3
6
0
0
0
0
5
2
0
5
4
0
5
6
0
2
e
-
5
2
.
5
e
-
5
3
e
-
5
3
.
5
e
-
5
C - Production
Time Hours
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
B
-
F
e
e
d

R
a
t
e
B
-
P
r
o
d
u
c
t
C
1
.
5
e
-
5
2
e
-
5
2
.
5
e
-
5
3
e
-
5
-
0
.
0
5
0
0
.
0
5
0
.
1
0
.
1
5
0
.
2
Feed Disturbance with Simple PID
Control
Feed Disturbance with Simple PID
Control
Stream Results
Ti me Hours
0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5 2.75 3
P
r
e
s
s
u
r
e

N
/
m
2
T
e
m
p
e
r
a
t
u
r
e

K
M
o
l
a
r

F
l
o
w

r
a
t
e

k
m
o
l
/
s
3
7
0
0
0
0
3
8
0
0
0
0
5
2
0
5
4
0
5
6
0
5
8
0
1
.
5
e
-
5
2
e
-
5
2
.
5
e
-
5
3
e
-
5
3
.
5
e
-
5
C-Production
Time Hours
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
B
-
F
e
e
d

R
a
t
e
B
-
P
r
o
d
u
c
t
C
1
.
5
e
-
5
2
e
-
5
2
.
5
e
-
5
3
e
-
5
-
0
.
0
5
0
0
.
0
5
0
.
1
0
.
1
5
Conclusion and Future Work Conclusion and Future Work
TAME Tower
Collect Data
Validate Models
Developing Advanced
Models
Improvements
New chemical system
Adjust for better dynamic
studies
Novel System
Validate Dynamic Models
Develop Control
Algorithms
Comparison of Reaction Rates
-0.06
-0.05
-0.04
-0.03
-0.02
-0.01
0
0.01
0.02
0.03
0.04
0.05
1 2 3 4 5 6 7 8 9
1
0
1
1
1
2
1
3
1
4
1
5
Stage (Condenser=1)
R
e
a
c
t
i
o
n

R
a
t
e
s

(
l
b
m
o
l
/
h
r
)
RADFRAC
RateFRAC
C-Production
Time Hours
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3
B
-
F
e
e
d
R
a
t e
B
-
P
r
o
d
u
c
t
C
1
.
5
e
-
5
2
e
-
5
2
.
5
e
-
5
3
e
-
5
-
0
. 0
5
0
0
.
0
5
0
.
1
0
.
1
5