Beruflich Dokumente
Kultur Dokumente
R EACTOR E NGINEERING
Volume 6
2008
Article A113
Azam Kavianiboroujeni
Abstract
An industrial ammonia synthesis reactor was studied in order to optimize its
operational conditions by means of increasing overall ammonia production. A heterogeneous, one-dimensional model and a two-dimensional rigorous model were
utilized to evaluate the process behavior. The simulation results of the two models
were compared with data from an industrial ammonia plant. The one-dimensional
model was found to be adequate for optimization purposes. Applying the Genetic Algorithm (GA) as a powerful method for complex problems, the model
was employed to optimize the reactor performance in varying its quench flows.
The optimal temperature profile along the fixed bed reactor was studied by changing independent variables including the quench temperature and the quench flow
rates. Optimization results show that the optimum quench temperature is about
615 K and that the optimum quench flows can enhance ammonia production rate
by 3.3%.
KEYWORDS: ammonia synthesis, fixed bed reactor, optimization, simulation,
genetic algorithm
The financial support of the Iran National Petrochemical Company-Research and Technology
Department is greatly acknowledged. Dr. M.R. Jafari-Nasr, head of the research group and Dr. A.
Taeb and Dr. V. Hadadi-Asl, head of the NPC-RT company are highly appreciated for their help.
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
1. INTRODUCTION
Ammonia is produced via an exothermic reversible reaction of hydrogen and
nitrogen. The process takes place over an iron-promoted catalyst structure. The
reaction synthesis is straightforward with no side reaction between the
components. It gives a stable product that can be described by the overall reaction
of:
N2 + 3H2 2NH3
(1)
the ammonia production at exit point of the fourth fixed bed inside the reactor.
This was done by varying the quench streams introduced between the catalytic
beds. The reactor configuration is described and modeling of the reactor with the
way of solving the differential equations as well as the reactor optimization
procedure is presented.
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
3. MATHEMATICAL MODELS
Two types of models were examined simulating the reactor including a one
dimensional as well as a two dimensional model.
Basic equations include the energy and mass balance equations for
ammonia component along the reactor. The two equations can be derived as
below.
Considering an element of dx in axial direction of the bed by having the
bed area, mass balance equation in steady-state condition can be inscribed as
following equation:
(2)
R NH 3
dZ
=
dx 2 FNo2 / A
(3)
(4)
dT
+ (H r ) R NH 3 = 0
dx
(5)
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
In contrast, the more rigorous two-dimensional model was based on the following
assumptions:
Steady state condition
Intra-particle mass and heat transfer restrictions considered by a term
called effectiveness factor
Concentration and temperature of the gas flowing through the catalyst
beds are equal to the catalyst particle at each location.
Dispersion of mass and energy in radial direction are not negligible
Considering constant density along the reactor
Independent solution of the equations to the angular direction due to the
radial direction symmetry
The catalytic activity along the reactor is uniform and equal to unity.
Based on the above assumptions, the basic equations comprising energy
and mass balances for ammonia synthesis reactor can be derived. The energy and
mass balance equations for a cylindrical differential element of the catalytic bed
can be given as below:
k eff
2T
T 1
T
+ C p u
k eff
= b R NH 3 (H r )
2
x r
r
r
(6)
- Deff
2w
w 1
w
+u
Deff
= b R NH 3
2
x r
r
r
(7)
for all r
r = rout
T=T0
&
w=w0
w
=0
r
&
T
=0
r
for all x
(8)
w
=0
r
RNH3, used in the model was reported by Dyson and Simon (1968) as
following relation:
RNH 3
= 2k K a2
aN2 (
Where ai =
ai =
a H2
2
a NH
3
) (
2
a NH
3
a H3 2
)1
(9)
fi
and the reference fugacity = 1 atm
fi 0
fi
= f i = y i i P
1
(10)
+ 1 .848863 10 T +
T
2
2001 .6
(11)
+ 2 .689
Since the catalyst particles are not sufficiently small, interaction of kinetic
and transport effects may not be ignored. The effect of the resistance due to
diffusion is expressed by the effectiveness factor calculated from an empirical
relation as follows. The polynomial used for the Fe catalyst having the size of 610 mm, depends on the three parameters of temperature, pressure and nitrogen
conversion as noted by Gaines (1979).
= b0 + b1T + b2Z+ b3T2+ b4Z2+ b5T3+ b6Z3
(12)
= 0.54526 +
+
3
T
T
(13)
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
P = 2 u =
150(1 ) u
1 u2
1
.
75
3
d p2
3 dp
(14)
4. SIMULATION RESULTS
Reactor specifications and operating conditions obtained from an operational
petrochemical ammonia plant used to simulate the Kellogg ammonia synthesis
reactor are given by Sadeghi (2004) as presented in Table 1.
Table 1: The plant data used for simulation of the ammonia synthesis reactor
Quench Temperature
Reactor ID
Reactor OD
First Bed Length
Second Bed Length
Third Bed Length
Fourth Bed Length
Syngas (feed) composition
yN2
yNH3
yH2
yCH4
yAr
Gas flow to first bed
First quench flow
Second quench flow
Third quench flow
650 K
0.18 m
1.48 m
1.1 m
2m
3m
4m
0.2363679
0.0269300
0.6567005
0.0597143
0.0202874
75000 kg/h
56500 kg/h
61000 kg/h
32000 kg/h
Simulation results show that the reactor conditions vary within the four
beds. Figure 2 shows how ammonia concentration changes along the beds. The
discontinuities occurring in the profiles are due to the injection of the quench
flows between the beds. The quench flows reduce the ammonia concentration at
the end of each bed however, it will develop along the next bed. While the first
bed has the smallest length, it is responsible for most of the changes in
concentration. In contrast little change in the concentration is due to the fourth
bed which has the highest length.
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
First bed
501.5
505.58
502.85
Second bed
490
494.77
491.88
Third bed
481.5
487.35
482.25
Fourth bed
475.3
482.56
476.45
10
(15)
Where fout and yout are reactor outlet flowrate and ammonia mole fraction
respectively.
Constraints prevailing the system can be described as outlined below:
1. Hotspots along the reactor must be avoided. Hence temperature should be
under 800K as stated by Shahrokhi and Baghmisheh (2005).
T < 800K
(16)
x + x
(17)
3. Temperature of the outlet hot stream leaving the heat exchanger at the top
of the reactor must be more than the temperature of cold stream entering
the first bed.
(18)
Ti < To
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
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50
Selection method
Crossover fraction
Mutation fraction
Roulette
.95
.05
Maximum generation
100
Figure 5: Ammonia production at the stream leaving the fourth bed for different
temperatures
The result shows that it is not possible to increase the amount of ammonia
production in the reactor by changing the quench temperature. An increase or
decrease in the quench temperature causes decline of ammonia production and
nitrogen conversion. Similar trend for nitrogen conversion profile in the reactor
was obtained.
Optimization of quench stream quantities is also studied with the aim of
enhancing the reactor performance. Ammonia production profile under optimal
condition for the fourth bed is depicted in figure 6. It shows the amount of
ammonia at the end of reactor in optimized condition has considerably improved
compared to normal operation reaching the value of 0.479. The Genetic
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
Algorithm parameters used in finding the optimal quench streams are given in
Table 4.
Table 4: Genetic algorithm parameters used to find optimal quench configuration
Population Size
Selection method
Crossover fraction
Mutation fraction
Maximum generation
100
Roulette
0.8
0.2
200
Figure 6: Ammonia production at the stream leaving the fourth bed for normal
and optimum quench flows
Comparison of the results for normal versus optimum conditions confirms
that since the amount of inlet gas increases in optimum condition, temperature
would decreases. The value of temperature deviation enlarges along the reactor as
shown in figure 7.
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Figure 8: Nitrogen conversion along the beds in normal and optimum conditions
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
The total quench flows has increased by 1.28 times from 41.54 to 53.07
kg/s at the optimum flow condition. This results in the ammonia production to
increase from 0.4628 to 0.4786 kgmole/s that equals to 3.4% increase in each
pass. Ammonia concentration also enhances from 0.0836 to 0.0842. This
improves the daily ammonia production by 23,207.04 kg which is a substantial
amount in yearly production (8,470 tons per year).
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6. CONCLUSION
An industrial ammonia synthesis reactor has been numerically studied for
optimization of operational condition in order to maximize ammonia production
yield. The optimization problem includes two approaches. In first approach,
optimal temperature profile along the reactor was calculated among feasible
quench temperature. In the second approach, by changing quench flows between
the fixed beds optimal quench flows were obtained. The optimal temperature
trajectory along the reactor and optimal flows yield 3.3% additional ammonia
production during one pass of synthesis gas into the reactor.
NOMENCLATURE
A
C
Cp
Deff
dP
FN A
f
fout
ID
k
K
OD
P
R
R NH 3
fugacity, atm
reactor outlet flowrate, mol/s
reactor inside diameter, m
reaction constant
equilibrium constant
reactor outside diameter, m
reactor pressure, atm
radial coordinate in reactor, m
reaction rate, kmol/kg catal.hr
T
u
w
x
yi
yout
Z
reactor temperature, K
velocity, m/s
mass fraction
axial coordinate in reactor, m
mole fraction of component i
ammonia mole fraction
nitrogen conversion
Greek letters
activity of component i
void fraction in catalyst bed
Sadeghi and Kavianiboroujeni: Optimization of Ammonia Synthesis Reactor using Genetic Algorithm
b
r
i
effectiveness factor
dynamic viscosity, Pa.s
gas density, kg/m3
bed density, kg/m3
heat of reaction, kJ/kmol
fugacity coefficient of component i
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