Modeling of Reactive Distillation

John Schell Dr. R. Bruce Eldridge Dr. Thomas F. Edgar

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
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

5. Design Tower - Size reaction zone

Catalyst requirements Column diameter

2. Pressure 3. Location of Zone 4. Estimate Catalyst

- Isothermal Plug-flow reactor with ideal separators

- 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
Exothermic Equilibrium Limited
45-62% at 50-80 C
MeOHSa m MeOH  Sa TAMESa m MeOHSa  2M1B
KB1 KB 2

Azeotropes Catalyst: Amberlyst-15

Methanol can inhibit rates. Rihko and Krause (1995)

TAMESa m MeOHSa  2M2B

KB3

KB 4

TAMESa m TAME  Sa 2M2B m 2M1B

KB5 KB6

Sa is a vacant adsorption site.

Pilot Plant (SRP)

0.152-meter diameter column Finite reflux 7 meters of packing in 3 sections Fisher DeltaV Control Kochs Katamax packing
C5 from Cat Cracker Pre-Reactor Makeup MeOH TAME Mixing Tank Unreacted C5, MeOH Reactive Distillation Column Recycle Back - Cracking Reactor 3.7 atm

SRP Pilot Plant

Koch Spool section, Katamax, Catalyst SRP - $145K

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

Trayed Tower: Equilibrium Model
L j 1 xi , j 1  V j 1 yi , j 1 ! L j xi , j  V j yi , j  Ri , j yi ! Kxi

Packed Tower: Continuous Model

x xi L ! AN iL  Yi AJL Rk xz k

Rate Model

N iV ! N iL

TAME Reaction Rates

Comparison of Reaction Rates
0.05 0.04 0.03 RADFRAC RateFRAC

Reaction Rates (lbmol/hr)

0.02 0.01 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 -0.01 15

Stage (Condenser=1)
-0.02 -0.03 -0.04 -0.05 -0.06

TAME Concentration Profile

Comparison of TAME Profiles
0.90 0.80 0.70 0.60

Mole Fraction

0.50 0.40 0.30 0.20 0.10 0.00 1 2 3 4 5 6 7 8 9 10 11 12 13 14 RADFRAC RateFRAC

Stage (Condenser=1)

15

Effective Reaction Rate

Traditionally simulations use intrinsic reaction rate. Effective rate is a function of intrinsic rate and diffusion limitations.

Effective Rate Molefraction

Control for TAME Tower Tower

Fisher DeltaV
Visual Basic Matlab, Visual Studio

Control Algorithms
PID Linear MPC Non-Linear MPC

State Estimation
Temperature Profiles Online Analyzers

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

A + B C1 C2
50 45 40 35

C1 C3
Isomer Distribution for Reactive Systems
Plug-flow Reactor CD Column

Exothermic Kinetics from CSTR Experiments Feed is dominated by inerts Replace hazardous heterogeneous catalyst

Mole %

30 25 20 15 10 5 0 1 2 3 4 5

Isomer

Novel System Data

Standard Conditions at 50 psig Over 26 Experiments
25 High Low Average Standard Deviation Temperature (C)

20

15

10
Reactive Zone

0
Overhead DA-220-1 DA-220-2 DA-220-3 DA-220-4 Vapor Temp TI-215 DA-210-1 DA-210-2 DA-210-3 DA-210-4 Reboiler Temp

Novel System Data

Profiles for 35 psig at Standard Conditions
25

Hi Lo Average Stnd Dev

20

Temperature (C)

15

10

Reactive Zone
5

0 Overhead DA-220-1 Vapor Temp 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

Simulation Validation - 50 psig

Column Data and Simulation for Standard Flows at 50 psig

Temperature (C)
0

10

15

20

25

Simulation Validation 35 psi

Simulation and Data for Standard Flows at 35 psig

Temperature (C)
0

10

15

20

25

Effect of Pressure
Effect of Varying Pressure
25 psig 35 psig 50 psig 75 psig

Temperature (C)
1 2

10

11

12

13

14

15

16

17

18

19

20

21

22

23

Effect of Varying Feed Rate

Effect of Varying Reactant Feed Rates

Temperature (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

10

11

12

13

14

15

16

17

18

19

20

21

22

23

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

Formerly Speed-Up and DynaPlus Equation Solver Aspen Properties Plus Tear Variables automatically selected Solves Steady-State and Dynamic Dynamic Events and Task Automation
Equations vs. Variables
1 1 2 3 4 5 6 7 8 9 10 T T T T X X 2 X X X X X X X X T T X X T T T T T T T T T T T T T T X X 3 4 5 6 7 8 9 10

Validation of Dynamic Simulator

Comparison of ACM and Aspen Plus Radfrac Results

ACM w/Tear Aspen Plus

Temperature (C)
1

10 11 12 13 14 15 16 17 18 19 20 21 22 23

Feed Disturbance With Manual Control

3e-5 0.2 C - Production

C B-Product 0.05 0.1 0.15 -0.05 0

1.5e-5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

B-Feed Rate 2e-5 2.5e-5

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

Molar Flow rate kmol/s 2e-5 2.5e-5 3e-5 3.5e-5

Temperature K 540 560

Stream Results
Pressure N/m2 350000 360000 0

520

0.25

0.5

0.75

1.25

1.5 1.75 Time Hours

2.25

2.5

2.75

Control of Reactive Distillation

Configurations
DB LV BV, LB
D R

Goals
Conversion Product Purity

Duty

Control of Reactive Distillation

Bartlett and Wahnschafft (1997)
Simple Feed-Forward/ Feed-Back PI Scheme

Kumar and Daoutidis (1999)

Showed linear controllers unstable for ethylene glycol systems Demonstrated possible Nonlinear MPC scheme

Sneesby et al. (1999)

Two point control with linear conversion estimator

Dependency of Conversion on Reboiler Duty and Reflux Ratio

Conversion vs Reboiler Duty

1

Conversion of Olefin for Molar Reflux Ratio of 1.9

0.9

0.8

0.7

0.6

Conversion

0.5

0.4

0.3

0.2

0.1

Reboiler Duty (MMkcal/hr)

Single Tray Conversion Estimation

Dependency of Conversion on Temperature
400 350 T8 T6

300

Temperature (C)

250

200

150

100

50

0 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00

Conversion

Single Tray Purity Estimation Single Tray Purity Estimation

Temperature (C)
230 0.00000E+00 5.00000E-08 1.00000E-07 1.50000E-07 235 240 245 250 255 260 265

Benzene Concentration

Purity of Alkylate

2.00000E-07

2.50000E-07

3.00000E-07

T8

T6 T7

3.50000E-07

4.00000E-07

4.50000E-07

5.00000E-07

Feed Disturbance With Manual Control

3e-5 0.2 C - Production

C B-Product 0.05 0.1 0.15 -0.05 0

1.5e-5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

B-Feed Rate 2e-5 2.5e-5

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

Molar Flow rate kmol/s 2e-5 2.5e-5 3e-5 3.5e-5

Temperature K 540 560

Stream Results
Pressure N/m2 350000 360000 0

520

0.25

0.5

0.75

1.25

1.5 1.75 Time Hours

2.25

2.5

2.75

Feed Disturbance with Simple PID Control

0.15 B-Feed Rate 2e-5 2.5e-5 C B-Product 0.05 0.1 3e-5

C-Production

-0.05

1.5e-5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Molar Flow rate kmol/s 2e-5 2.5e-5 3e-5 3.5e-5

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9

580

Stream Results
Pressure N/m2 370000 380000 0

1.5e-5

520

Temperature K 540 560

0.25

0.5

0.75

1.25

1.5 1.75 Time Hours

2.25

2.5

2.75

Conclusion and Future Work

TAME Tower
Collect Data Validate Models Developing Advanced Models Improvements
New chemical system Adjust for better dynamic studies
Reaction Rates (lbmol/hr)

Comparison of Reaction Rates

0.05 0.04 0.03 0.02 0.01 0 10 11 12 13 14 -0.01 15 1 2 3 4 5 6 7 8 9 RADFRAC RateFRAC

Stage (Condenser=1)
-0.02 -0.03 -0.04 -0.05 -0.06

Novel System
Validate Dynamic Models Develop Control Algorithms

-0.05

1.5e-5

B-Feed Rate 2e-5 2.5e-5

C B-Product 0.05 0.1

3e-5

0.15

C-Production

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 Time Hours

2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9