Fischer-Tropsch Reactor Model in VBA for Excel

Kyle Brunner, Caleb Miskin, Joseph Bell, Calvin Bartholomew, William Hecker
Objective: Develop and validate a 1-D Fixed-bed reactor model that accurately reflects industrial reactor behavior
Model Description
The reactor model is a shell and tube heat exchanger with catalyst pellets on the tube side
and high-pressure boiling water on the shell side. The user specifies the final CO
conversion and the VBA code solves the design equations
1,2
by a 4th order Runge-Kutta
algorithm at fixed steps (typically 3 mm) down the reactor until the desired conversion has
been reached. Kinetic equations, catalyst geometry, catalyst properties, and reactor
conditions are user inputs.
Model Validation
Partial validation using Shell Bintulu plant data
9 design parameters constrained by the Shell report
7 design parameters assumed/adjusted
3 of 4 performance parameters matched within 10% of reported values
Model Characterization
Industrial Significance
Fischer-Tropsch (FT) synthesis has been
commercial since WWII
FT technology has become a viable alternative
source of liquid fuels due to concern over foreign
oil dependence and fuel prices
Feed stocks include natural gas, coal, biomass,
and garbage.
Fixed-bed design is simplest and most economical
for smaller scale production
This model demonstrates ability to:
Develop relatively cheap, robust codes
Gain insight into reactor design issues
Explore ranges of operating parameters

1Davis, M. E. et al, Fundamentals of Chemical Reaction Engineering; McGraw Hill: Boston, 2003.
2Froment, G. F.; Bischoff, K. B. Chemical Reaction Analysis and Design; 2nd Edition; Wiley Series in Chemical Engineering: New York, 1990; pp. 620-625.
3C. H. Bartholomew and R. J. Farrauto, Industrial Catalytic Processes; 2nd Edition; John Wiley & Sons, Inc., New Jersey, 2006. Chapter 6 & p. 459
Hydrocarbon
Products
Waste Water &
Some Lighter HCs
Methane &
Waste Gasses
CO & H2 Feed
Liquid Recycle
Gas Recycle
Fixed-
bed FT
Reactor
Hot
Trap
Cold
Trap
www.icat.dtu.dk/intro/index.html
r A
dz
dF
A b o C
A
) ( v q =
) (
4
) ( ) (
*
0 T T
d
U
r H
dz
dT
C u
t
A b o T r p
A = v q
c g
L
GW
g
dz
dP

c c
o

=
3 '
) 1 (
*C = 0.002366 (atm-y); AHc = -17,883 (J/mol)

Data Source Rate Expression Form
A
(atm-1.25s-1)
EA
(J/mol) B (atm-x)
AHB
(J/mol)
Generalized
(Cobalt)
1.27E+08 90,927 0.0750 -6,753
Generalized*
(Cobalt)
142 33,783 1.28E-09 -78,461
Critchfield
(Iron)
20,083 77,000 4.61E-03 -18,400
( )
2
2
3 1
2 4
CO H
2 1 1
2 4
CO H 1
CO
AP P
r
BP P
=
+
http://www.engin.umich.edu/~cre/01chap/html/reactors/sasol.htm
Parameter
Co/ZrO2/SiO2 (Shell)
Reported3 Assumed
Input/Operating Parameters
HC Production (bbl/day) 6,700
% CO 32.3
H2/CO Ratio 2.15
Inlet Temp (K) 468
Pressure in (bar) 40
Recycle Ratio 3.0
CO conversion (%) 75
C2+ Selectivity 96
CH4 Selectivity 4
CO2 Selectivity (% of CO
converted) 1
Reactor/Catalyst
Characteristics
Tube diameter (cm) 5.0
Number of tubes 8,000
Cooling water Temp (K) 460.5
Catalyst particle diameter (mm) 2
Bed void fraction 0.40
Catalyst activity 0.20
Output/Performance
Parameters Reported Calculated
Effectiveness factor 0.96
Space velocity (h1) 1,139
Pressure drop (atm) 0.28
Tube length (m) 20 19.4
Catalyst charge (m3) 310 301
Catalyst productivity
(gC5+/gcat-h) 0.092 0.12
Outlet or Maximum
Temp (K) 510 474
http://www.bda.gov.my/investment/Projects.htm
Figure 1. Effect of kinetic model on temperature profile for cobalt
catalysts with Twall held constant at 488 K.
Kinetic Model Study
Figure 3. Effect of inlet pressure on reactor length for cobalt catalysts
with constant Tmax at 497 K by varying Twall.
Pressure Study Particle Diameter Study
Figure 4. Effect of particle diameter on reactor length for cobalt catalysts of
various particle geometries with constant Tmax at 497 K by varying Twall.
Figure 2. Effect of recycle ratio on temperature profile for cobalt catalysts
with constant Tin = 490 K and Tmax = 500 K by varying Twall.
Recycle Ratio Study
0.00
10.00
20.00
30.00
40.00
50.00
60.00
0.000 0.001 0.002 0.003 0.004 0.005 0.006
Particle Diameter (m)
R
e
a
c
t
o
r
L
e
n
g
t
h
(
m
)
Spheres
Trilobe
Cylinder
Hollow Cylinder
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
15 20 25 30 35 40 45 50 55
Inlet Pressure (atm)
R
e
a
c
t
o
r
L
e
n
g
t
h
(
m
)
490
492
494
496
498
500
502
0 2 4 6 8 10 12 14
Reactor Length (m)
T
e
m
p
e
r a
t u
r e
( K
)
RR = 0 Tw 477.0 K
RR = 1 Tw 483.0 K
RR = 2 Tw 486.5 K
RR = 3 Tw 488.5 K
RR = 4 Tw 490.0 K
RR = 8 Tw 490.0 K
489.00
490.00
491.00
492.00
493.00
494.00
495.00
496.00
497.00
498.00
0 2 4 6 8 10 12
Reactor Length (m)
T
e
m
p
e
r a
t u
r e
( K
)
Model 1
Model 2
Model 3
Model 4
( )
2 2 / 1
2 / 1
2
2
1 H CO
H CO
CO
CP BP
P AP
r
+ +
=
( )
2 3 / 1 3 / 2
6 / 5 3 / 2
2
2
* 1 H CO
H CO
CO
P BP
P AP
r
+
=
Table 1. Representative Kinetic Models For Co and Fe Used in Model Validation