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simulated and actual reactor outlet temperature was The outlet product from first reactor is fed to the second
approximately 30%. Besides, the deviation of the simu- reactor. After passing through the four reactors in series,
lated total conversion from the plant data was approxi- the catalyst at the outlet of last reactor is sent to the
mately 25%.It was claimed that the error could be continuous catalyst regeneration unit. The catalyst is
reduced by increasing the calculation step number. then regenerated and recycled back to the first reactor
To date, the radial moving bed reactor modeling and for the next reaction cycle. The outlet temperature
simulation considering both the radial and axial varia- decreases since the process is highly endothermic. Inter-
tions for propane dehydrogenation was not reported in stage heaters are required to increase the inlet tempera-
the open literature. Chin et al. (2011) modelled the radial ture (Bijani and Sahebdelfar 2008; Gyngazova et al. 2011;
moving bed reactor by assuming it was plug flow reactor. Sahebdelfar et al. 2011; Farsi, Jahanmiri, and Rahimpour
The deviations of the predicted composition of H2, C2H4 2013).
and C2H6 from the plant data were 21%, 14% and 11%. It
was stated that these deviations may be attributed to the
omission of the variations of concentration, temperature 2.2 Plant data reconciliation
and reaction rate in the radial direction.
The aim of the present work is to model and simulate Industrial plant data was required to validate the model
a radial moving bed reactor for the propane dehydro- for propane dehydrogenation process. Thirteen sets of
genation considering both axial and radial variations. data were taken at different operating days. It consists
The industrial plant data was used to support the kinetic of inlet and outlet temperature, inlet and outlet pres-
parameter estimation and model validation. sure, inlet and inter-stage gas composition. Among
these data, only four sets of data were used to optimize
the reaction kinetic parameters due to its consistent
inter-stage gas composition. This data was obtained at
2 Model development and data different reactor operating conditions, which were
validation methodology denoted as Case 1, 2, 3 and 4. All the operating condi-
tions are given in range in Table 1 due to the confidenti-
ality of the plant data.
2.1 Radial moving bed reactor model
The commercial radial moving bed reactor for propane Table 1: Operating conditions of the reactor.
dehydrogenation consists of a series of four reactors as
shown in Figure 1. The reactor comprises two perforated Variable Value
coaxial cylinders to retain the catalysts. The feed gas Hydrogen to hydrocarbon molar ratio, H/HC .–.
enters from the bottom of first reactor and crosses (mole/mole)
radially through the catalyst bed that moves slowly *WAIT, °C –
downwards through the reactor by gravitational force. Inlet pressure, Pin (kPaG) –
The catalyst from the first reactor is then collected in Note: *WAIT is the weighted average inlet temperature; the integrated
the catalyst collector and lifted to the second reactor. temperature calculated using the inlet temperature of each reactor.
Product
= Catalyst line
= Gas Process line
R = Reactor
H = Heater
2.3 Mass balance Where CpA is the heat capacity of component A, ΔHRx, n, T
is the heat of reaction for reaction n at certain tempera-
Mass balance equations for radial moving bed reactor ture (T) and TRef is the reference temperature, 25°C. Data
were governed based on the incremental volume of for calculating the heat capacity and heat of reaction are
ring-shaped reactor bed as shown in Figure 2. These taken from Yaws (1999).
equations were shown in eqs (1) and (2).
k1
C3 H8 $ C3 H6 + H2 (6)
k−1
The energy balance in the incremental volume of catalyst bed 2.5.2 Side reactions
can be written as eq. (4) and it can be simplified as eq. (5).
X X Beside propane dehydrogenation, the elevated tempera-
FA CpA T − TRef jW − FA CpA T − TRef jW + ΔW
(4) ture in this process also promotes side reactions such
+ ðΔHRx, T Þ − rn′ ΔW = 0 propane cracking and hydrogenolysis. The propane is
cracked into methane and ethylene as a result of catalytic
dT ðΔHRx, n, T Þ − rn′
= P (5) cracking on the catalyst surface. Meanwhile, the propane
dW FA Cpa
is reacted with hydrogen to produce methane and ethane
through the hydrogenolysis reaction. Ethylene is then Kads = KA0 expð − ΔHA =RT Þ (18)
further hydrogenated to produce ethane (Chin et al.
Where ka0 and Ka0 are the exponential factor for kinetic
2011; Farjoo et al. 2011; Li et al. 2011; Sahebdelfar et al.
reaction and adsorption equilibrium constant, Ea is the
2012; Farsi, Jahanmiri, and Rahimpour 2013).
activation energy and ΔHa is the heat of adsorption.
The side reactions occurred during propane dehydro-
genation are described in eqs (9)–(10):
k2
C3 H8 ! CH4 + C2 H4 (9)
2.6 Numerical solution
k3
C2 H4 + H2 ! C2 H6 (10) In the present study, the catalyst bed is discretized into a
number of ring shapes at axial and radial directions. The
The rate equations for the proposed side reactions are discretized catalyst bed can be seen in Figure 3. The
shown in eqs (11)–(12). weight of discretized bed can be calculated using eq. (19).
− r2 = k2 PC3 H8 (11) W.Δz.Δr.½2R1 − ð2j − 1Þ.Δr
ΔWi, j = (19)
− r3 = k3 PC2 H4 PH2 (12) h. R22 − R21
C3 H8 ! 3C + 4H2 (13) Where, i and j are the number of elements in the axial
and radial directions respectively. R1 and R2 are the bed
nC3 H6 ! 3nCH0.5 + 2.25nH2 (14)
inner and outer radius, h is the height of catalyst bed, Δr
The coking rate on catalyst surface can be represented and Δz are the elemental ring thickness and the height of
by eq. (15). ring respectively.
Equations (2), (5) and (15) for mass balance, energy
da kc PC3 H6
− = a (15) balance and catalyst activity were discretized to eqs
dt Cm ð1 + Kads PH2 Þ
(20)–(22) before it was solved numerically to simulate
Where Cm is the total concentration of the active sites, the RMBR.
kc is the coking rate constant and Kads is the adsorption
′
equilibrium constants. Once the catalyst activity was FAji, j + 1 = FAji, j + ΔWi, j rnji, j (20)
obtained, coke formation can be calculated using eq. (16): ′
ðΔHRx, n, T Þ − rn
Cc = Cm ð1 − aÞ (16) Ti, j + 1 = Ti, j + 1 + ΔWi, j P (21)
FA CpA i, j
Where, Cc is the concentration of the active sites occupied
kd PC3 H8 ai, j W
by the coke. ai + 1, j = ai, j − (22)
1 + Kads PH2 Us
The kinetic rate constants and adsorption equilibrium
constants in this work were estimated based on Arrhenius
The boundary conditions adopted are:
and van’t Hoff equations as shown in eqs. (17)–(18):
at z = 0, að1st reactorÞ = 1
kA = kA0 expð − EA =RT Þ (17) at r = 0, F = Fin ;T = Tin
The calculation was started at the uppermost ring, Table 2: Kinetic constants of the proposed kinetic models.
from the inner radius to the outer radius, considering that
the feed gas entered the reactor from inner radius of the Parameter Value Unit
bed and the catalyst moved from top to bottom of the k1 k01 = 13.920 kmol/(kg.hr.kPa)
reactor. The inlet temperature of the first ring was used to E1 = 31.978 kJ/mol
calculate the reaction rate and outlet composition using k2 k02 = 1.573e6 kmol/(kg.hr.kPa)
eqs (7), (11)–(12), (17) and (20). The outlet temperature of E2 = 141.94 kJ/mol
k3 k03 = 3.3965 kmol/(kg.hr.kPa)
the first ring became the inlet temperature for the second
E3 = 149.41 kJ/mol
ring at the same row. It was calculated based on outlet
kd k0d = 1.097e-1 (kg.kPa.hr)−
composition at each ring using eq. (21). Catalyst activity Ed = 146.21 kJ/mol
for the first row was calculated based on the outlet tem- Kads K0ads = 5.553e-2 atm−
perature at each ring using eq. (22). These procedures ΔHads = 91.798 kJ/mol
were then repeated for the entire rings in the first row Cm = . g active site/g catalyst
Main Rx Side Rx
st
nd Side Rx
eq. () eq. () eq. ()
55 5.0
4.5
50
4.0
45
3.5
40
3.0
Mole fraction CH4
Mole fraction H2
35 2.5
35 40 45 50 55 2.5 3.0 3.5 4.0 4.5 5.0
H2 plant data mole fraction, % CH2 plant data mole fraction, %
(a) (b)
2.0 0.3
C2H6 predicted mole fraction, %
1.0 0.1
45
15
40
10
35
5
30
Figure 4: Parity plot of the plant and model predicted mole fractions of (a) hydrogen; (b) methane; (c) ethane; (d) ethylene; (e) propane and
(f) propylene.
The resultant propane conversion and selectivity were the observed plant data. The root mean square deviations
calculated and compared with the plant data as shown for propane conversion and selectivity are 0.55 and 1.5
in Table 4. It can be seen that the predicted propane respectively, demonstrating the accuracy of the consid-
conversion and selectivity have good agreement with ered model and assumptions.
0.1 0.006
Hydrogen Methane
0.08
0.004
Residual (data - predicted)
0.06
0.02 2E- 18
2 3 4 5
0
35 40 45 50 55 –0.002
–0.02
–0.04 –0.004
–0.06
Mole fraction plant data, % –0.006
Mole fraction plant data, %
(a) (b)
0.003 0.00050
Ethane Ethylene
0.002
Residual (data - predicted)
0 0.00000
0.5 1 1.5 2 0.00 0.05 0.10 0.15 0.20
–0.001
–0.00025
–0.002
–0.003 –0.00050
Mole fraction plant data, % Mole fraction plant data, %
(c) (d)
0.05 0.03
Propane
0.04 Propylene
0.02
0.03
Residual (data - predicted)
Residual (data- predicted)
0.02
0.01
0.01
0 0
5 7 9 11 13 15
–0.01 30 35 40 45 50
–0.01
–0.02
–0.03 –0.02
–0.04
–0.05 –0.03
Mole fraction plant data, % Mole fraction plant data, %
(e) (f)
Figure 5: Residual curve for (a) hydrogen; (b) methane; (c) ethane; (d) ethylene; (e) propane and (f) propylene.
3.2 Simulation results H2/HC was ± 0.7. The propane conversion profiles at axial
and radial directions for the 1st, 2nd, 3rd and 4th reactor
3.2.1 Propane conversion along radial and axial are shown in Figure 6.
directions Propane conversion increases significantly in the
radial direction because the gas flows radially. On the
The kinetic data obtained in the previous section was other hand, propane conversion slightly decreases along
adopted in the subsequent simulation studies. The the axial direction due the reduction in the catalyst activ-
WAIT of the radial moving bed reactor was ± 641°C and ity as it flows downward. The predicted conversion for 1st,
Propane Conversion, %
Plant data Model (125 kPa)
30
Propane conversion (%) Case . . 25
Case . .
20
Case . .
Case . . 15
2nd, 3rd, and 4th reactor were 15.032 %, 11.604 %, 7.696% Figure 7: Comparison of the equilibrium conversion with the
and 4.495% with the total conversion 33.8%. Deviations simulated conversion.
of the propane conversion for each reactor compared to
the plant data were 3.72%, 1.58%, 0.834% and 3.595%. Zangeneh et al. (2013). The catalyst activity decreased as
The decrease of propane conversion along the reactor it flowed through the reactors in series. Moreover, Figure 7
series in the present study can be analogous to the shows that the sensitivity of the equilibrium constant and
decrease of propane conversion with time as reported conversion to the temperature change is lower when its
by Kaneko et al. (2009), Sahebdelfar et al. (2012) and value is getting higher (Caspary et al. 1997).
18 15
z/L = 0 z/L = 0
15
Propane conversion, %mol
12
z/L = 2/3 z/L = 2/3
12
z/L = 1 9 z/L = 1
9
6
6
3
3
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Radial Position, (r-R1)/(R2-R1) Radial Position, (r-R1)/(R2-R1)
(a) (b)
10 8
z/L = 0 z/L = 0
Propane conversion, %mol
Propane conversion, %mol
2
2
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Radial Position, (r-R1)/(R2-R1) Radial Position, (r-R1)/(R2-R1)
(c) (d)
Figure 6: Propane conversion profile along the radial and axial directions for (a) 1st reactor; (b) 2nd reactor; (c) 3rd reactor and (d) 4th reactor.
3.2.2 Temperature profile along radial and axial decay as the catalyst flows along this direction.
directions Comparing to the plant data, the deviations of the pre-
dicted outlet temperature from the plant data of the 1st,
In the experimental study of propane dehydrogenation, 2nd, 3rd and 4th reactors are 3.41%, 4.44%, 3.87% and
the reactors were usually assumed to be an isothermal 2.08% respectively.
reactor under an average temperature (Praserthdam,
Grisdanurak, and Yuangsawatdikul 2000; Lobera et al.
2008b; Bijani and Sahebdelfar 2008; Farjoo et al. 2011). 3.2.3 Coke formation along radial and axial direction
The temperature gradient in both radial and axial direc-
tions can be obtained using process model considering Figure 9 shows the coke content of the catalyst at the
both of these directions. Figure 8 shows the temperature reactor in radial and axial directions. In the radial direc-
profile at different bed depth and radial distances. The tion, coke content at the inner radius is higher than the
trend of the temperature profiles in radial and axial direc- outer radius due to its higher temperature that promotes
tions are similar with the temperature profile of the coke formation through cracking. The endothermic reac-
endothermic isobutane dehydrogenation in a RMBR as tion occurred radially has caused the temperature drop at
predicted by Sahebdelfar et al. (2011). The temperature the outer radius. Similarly, the coke content increases
profile in radial direction declines along the flow direc- when the catalyst flows from the top to bottom of the
tion due to the highly endothermic reaction. The tem- reactor. More coke is deposited on the catalyst as it
perature difference between inner wall and outer wall moves downward because of the longer catalyst resi-
drops along the axial direction because of the catalyst dence time. The longer catalyst residence time also has
630 660
640
Reactor temperature, °C
Reactor temperature, °C
610
620
570 560
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Radial Position, (r-R1)/(R2-R1) Radial Position, (r-R1)/(R2-R1)
(a) (b)
650 650
640
Reactor temperature, °C
Reactor temperature, °C
640
630
630
z/L = 0
620 z/L = 0
z/L = 1/3
z/L = 1/3
z/L = 2/3 620 z/L = 2/3
610
z/L = 1 z/L = 1
600 610
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Radial Position, (r-R1)/(R2-R1) Radial Position, (r-R1)/(R2-R1)
(c) (d)
Figure 8. Reactor temperature profile along the radial and axial directions of (a) 1st reactor; (b) 2nd reactor; (c) 3rd reactor
and (d) 4th reactor.
2 3.2
(r-R1)/(R2-R1) =0 (r-R1)/(R2-R1) = 0
(r-R1)/(R2-R1) = 1/3 (r-R1)/(R2-R1) = 1/3
(r-R1)/(R2-R1) = 2/3 2.8
1.5 (r-R1)/(R2-R1) = 2/3
(r-R1)/(R2-R1) =1
Coke Content, wt%
0.5
1.6
0
0 0.2 0.4 0.6 0.8 1 1.2
0 0.2 0.4 0.6 0.8 1
Axial Position, z/L Axial Position, z/L
(a) (b)
3.8 4.4
(r-R1)/(R2-R1) =0 (r-R1)/(R2-R1) =0
3.6 (r-R1)/(R2-R1) = 1/3 4.2 (r-R1)/(R2-R1) = 1/3
(r-R1)/(R2-R1) = 2/3 (r-R1)/(R2-R1) = 2/3
3.4 Coke Content, wt% (r-R1)/(R2-R1) =1
Coke Content, wt%
2.4 3.2
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Axial Position, z/L Axial Position, z/L
(c) (d)
Figure 9: Coke content on the catalyst active site along the radial and axial directions of (a) 1st reactor; (b) 2nd reactor; (c) 3rd reactor
and (d) 4th reactor.
caused an increase in coke content along the reactor constants were optimised before it was used to simulate
series. the propane conversion, reactor outlet temperature, coke
The coke contents at the outlet of 1st, 2nd, 3rd and 4th formation and the corresponding catalyst activity in the
reactor are found to be 1.32%, 2.49%, 3.33% and 3.98% radial and axial directions of all reactors.
respectively. The coke content at the outlet of the last It was found that the predicted activation energies of
reactor well matches with coke content measured from the propane dehydrogenation (31.978 kJ/mol), propane
the plant. The corresponding catalyst activity profiles are cracking (141.94 kJ/mol) and ethylene hydrogenation
shown in Figure 10. Lower catalyst activity is attributed to (149.41 kJ/mol) were in reasonable agreement with the
the higher coke content. The catalyst activities at the experimental values reported in the literature. The model
reactor outlets of the 1st, 2nd, 3rd and 4th reactor are validity check using the parity plot and residual analysis
0.758, 0.543, 0.39 and 0.267 respectively. of the component compositions concluded the adequacy
of the model.
The model developed has accurately predicted the
4 Conclusion reaction temperature profile, conversion profile and cat-
alyst coke content. The corresponding catalyst activity
The present study aimed to develop and validate a first after the 4th reactor in the series was 0.267. The model
principal model for propane dehydrogenation catalysed can be further used to optimise the process for obtaining
by platinum on alumina in a RMBR. The reaction kinetic higher production yield.
1 0.8
0.95 0.75
0.9 0.7
Catalyst Activity
Catalyst Activity
0.85 0.65
0.8 0.6
0.75 0.55
(r-R1)/(R2-R1) =0 (r-R1)/(R2-R1) = 0
0.7 (r-R1)/(R2-R1) = 1/3 0.5 (r-R1)/(R2-R1) = 1/3
(r-R1)/(R2-R1) = 2/3 (r-R1)/(R2-R1) = 2/3
0.65 0.45
(r-R1)/(R2-R1) =1 (r-R1)/(R2-R1) = 1
0.6 0.4
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
Axial Position, z/L Axial Position, z/L
(a) (b)
0.55 0.4
0.5
0.35
Catalyst Activity
Catalyst Activity
0.45
0.3
0.4
(r-R1)/(R2-R1) = 0 (r-R1)/(R2-R1) =0
(r-R1)/(R2-R1) = 1/3 (r-R1)/(R2-R1) = 1/3
0.25
0.35 (r-R1)/(R2-R1) = 2/3 (r-R1)/(R2-R1) = 2/3
(r-R1)/(R2-R1) = 1 (r-R1)/(R2-R1) =1
0.3 0.2
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Axial Position, z/L Axial Position, z/L
(c) (d)
Figure 10: Catalyst activity along the radial and axial directions of (a) 1st reactor; (b) 2nd reactor; (c) 3rd reactor and (d) 4th reactor.
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