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CFD Study of Diesel Oil Hydrotreating Process in The Non-Isothermal Trickle Bed Reactor
CFD Study of Diesel Oil Hydrotreating Process in The Non-Isothermal Trickle Bed Reactor
a b s t r a c t
In the present study, the EulerianEulerian multiphase approach was implemented to simulate the hydrotreating
processes (hydrodesulfurization (HDS) and hydrodearomatization (HDA)) in the trickle bed reactor (TBR) by means of
computational uid dynamics (CFD) technique. A new gasliquid interphase heat transfer coefcient was used in the
CFD model to predict the reactor performance at non-isothermal conditions. The effects of feed inlet temperature,
gas and liquid velocities, operational pressure and hydrogen sulde concentration of the gas phase were investigated
to calculate the reactions conversions and the bed temperature distribution. Also, the inuence of bed porosity and
adiabatic operational conditions on the reactor temperature and HDS reaction conversion was discussed. The results
showed at adiabatic reactor, HDS reaction conversion increased about 9% compared to constant wall temperature
condition. Furthermore, it was found that neglecting the gasliquid interphase heat transfer effect in the CFD model
increases the average relative error between numerical and the experimental data at prediction of HDS conversion
about 5% and also affects the bed temperature pattern.
2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords:
Computational uid dynamics (CFD); Hydrotreating; Non-isothermal condition; Trickle bed reactor;
1.
Introduction
550
Nomenclature
a, b and C constants (dimensionless)
specic gasliquid interface (m1 )
aGL
as
specic surface of a particle (m1 )
concentration of ith species at liquid phase
CL,i
(mol/m3 )
heat capacity (J/kg K)
Cp
diffusion coefcient (m2 /s)
D
dp , dh , dr particle, hydraulic and reactor diameter (m)
Ergun constants
E1 , E2
2
Etvs number Eo = L g(dh ) / in Eq. (14)
Eo
(dimensionless)
Eo
modied Etvs number (dimensionless)
interphase momentum exchange coefcient
F
(kg/m3 s)
fe
wetting efciency (dimensionless)
Froude number (dimensionless)
Fr
gravity (m/s2 )
g
Henrys coefcient (MPa cm3 /mol)
H
specic enthalpy (W/m3 )
h
hG,L
gasliquid interphase heat transfer (W/m2 K)
modied Galileo number (dimensionless)
Ga
K
mass transfer coefcient (m/s)
KPoly/Di/Mono dynamic equilibrium constant (dimensionless)
Kw
Watson characterization factor (dimensionless)
thermal conductivity (W/m K)
k
ks
HDS reaction constant (((m3 )2.16 )/kg(kmol)1.16 s)
k,k
forward and backward reaction rate constants
(m3 /kg s)
kad
HDS reaction adsorption coefcient (m3 /kmol)
liquid hourly supercial velocity (h1 )
LHSV
m
interphase mass transfer rate (kg/m3 s)
Nu
Nusselt number (dimensionless)
Prandtl number (dimensionless)
Pr
Reynolds number, Re = U dh / in Eq. (14)
Re
(dimensionless)
Re
modied Reynolds number (dimensionless)
pressure (Pa)
P
q
heat ux (W/m2 )
R
universal gas constant (J/mol K)
reaction rate of ith species (kg/m3 s)
Ri
r
radius (m)
source term (kg/m3 s)
S
SG
specic gravity (dimensionless)
temperature (K)
T
cubic average boiling point (K)
TCABP
TMABP
molal average boiling point (K)
TMeABP mean average boiling point (K)
t
time (s)
velocity (m/s)
u
v
molar volume (m3 /mol)
mass fraction (dimensionless)
x
molar fraction (dimensionless)
xmi
Greek symbols
, and constants (dimensionless)
, and constants (dimensionless)
HR
heat of reaction (J/mol)
Subscripts
b
boiling point or bulk porosity
gas
G
ith species
i
int
interaction
kth phase
k
liquid phase
L
pressure
P
r
rth phase
solid phase
S
T
temperature
551
2.
Governing equations
2.1.
Modeling assumption
forms:
G
=
G + L
FGL
(1)
i=r
(k k uk )
+ (k k uk 2 ) = k Pk + (k uk ) + k k g
t
+
k
rk ukr m
kr ) + Fint,k (uk ur )
(urk m
G 2 dp 2
S
(1 G )
G
G + L
E1 G (1 G )
G 2 dp 2
1
G + L
E1 G (S )
L 2 dp 2
0.333
S
(1 G )
FLS =
0.667
(5)
0.667
0.333
E2 L uL (S )
L dp
(6)
(7)
2.3.
rk,i m
kr,i ) + fe k Rk,i
(m
(8)
i=r
(k k )
rk m
kr ) + Sq
(m
+ (k k uk ) =
t
E2 G uG (1 G )
S
+
G dp
(1 G )
Hydrodynamics equations
To develop the momentum, mass and heat equations the following assumptions were regarded as:
2.2.
E1 G (1 G )
E2 G (uG uL )(1 G )
S
+
G dp
(1 G )
FGS =
(2)
i=r
(3)
(4)
The correlations required for calculation of species molecular diffusion, Di , and interphase mass transfer are presented
in Table 1. Also, diesel oil component concentration and distillation information are tabulated in Table 2.
In the current work, molecular diffusion was used to
describe mass diffusion instead of packed beds axial and
radial dispersion coefcients, Eq. (8). According to Ranade
et al. (2011) main factors contributing to mass and liquid
dispersion in the packed beds are non-uniform porosity distribution, partial wetting, dead-zones and channeling. These
factors have the vital effects on dispersion in the trickle bed
reactors. The main idea to develop axial and radial mass dispersion (diffusive term) models in the packed beds is the
investigation of hydrodynamics and porous media effects on
species governing equations (Jarullah et al., 2012b; Mederos
and Ancheyta, 2007; Mederos et al., 2006, 2009a, 2012). Therefore, in the models in which hydrodynamic and bed properties
(porosity distribution, partial wetting, dead-zones and channeling) are regarded, using axial or radial dispersion coefcient
causes over prediction of species diffusion terms and reactor
performance. Here, it should be noticed that in the packed
beds with large particles diameter, mechanical dispersion cannot be fully explained by porosity distribution functions and
appropriate models need to be used to improve the mathematical description of the reactor. In this work, due to small
particles size, the effect of mechanical dispersion was ignored
in the CFD model.
The ability of EulerianEulerian multiphase approach on
evaluation of axial and radial dispersion was studied by different researchers (Atta et al., 2007a; Bazmi et al., 2012;
Gunjal et al., 2003). They found a good agreement between
552
Table 1 Correlations to estimate diesel oil properties, bed characteristics and interphase mass transfer correlations.
Parameter
Correlation
L = 0 + P + T
i or L
TMeABP =
0.2896
vcL = 0.5567TMeABP
SG0.7666
15.6
TMABP + TCABP
,
2
TCABP =
v0.267
T
L
v0.433 L
1
1.8
n
TMABP =
n
xmi Tbi
i=1
i (1.8Tbi 459.67)
i=1
1/3
PG,i
LG,i = m
GL,i i : H2 or H2 S
CL,i , m
i
H
0.5
2
KL,i aL
L uL
L
= 1.8
i : H2 or H2 S
DL,i
L
L DL,i
vi
Hi =
i : H2 or H2 S
i L
2
(T 273.15)
1
2
H2 = 0.5597 0.4294 103 (T 273.15) + 3.0753 109
+ 1.944 106 (T 273.15) + 0.835 103
106
20 C
20 C
Bed porosity
function (Bazmi
et al., 2011)
(constants were
selected for sock
bed)
k = 1.7307(1.8 TMeABP ) SG15.5 C
= exp(21.78 8.07986t + 1.12981t2 0.05309t3 )
= 4.13948 + 1.29924t 0.17813t2 + 0.00833t3
= 0.19876 0.0312t 0.00567t2
t = (1.8T 460)/100
Cp = ( + T)
= 1.4651 + 0.2302 Kw
= 0.306469 0.16734 SG15.5 C
= 0.001467 0.000551 SG15.5 C
1/3
Kw = ((1.8 TMeABP ) )/SG
15.5 C
= (b + D) + (1 (b + D))
exp
C dr
p
3
2
ai (r/dp )2
(r/dp )(3+2(i1)) +bi
i=1
i
1
2
3
a
1.803
1.185
0.02649
b
0.0479
0.3566
0.001925
C
0.1252
D
0.045
P = ([0.167 + 16.181 100.04250 ][P 1.450 107 ] 0.01 [0.2999 + 263 100.06030 ] [P 1.450 107 ] ) 16.018
2.54
2
T = ([0.0133 + 152.4(0 + P )
](T 1.8 520) [8.1 106 0.0622 100.764(0 +P ) ](T 1.8 520) ) 16.018
3.444
a
L = 3.141 107 (T 1.8 460)
[log 10 (API)]
a = 10.313[log 10 (T 1.8 460)] 36.447
141.5
API =
131.5
SG15.6
4
= (0.0017237 Tb0.05873 SG0.64927 (L G )) /1000
0.014
0.185
0.025
fe = 0.335Re L Eo 0.188Ga G (1 + FrG )
553
Components
Monoaromatics
Diaromatics
Triaromatics
17.96
8.77
1.64
Tetraaromatics
Naphthenes
Parafn
0.95
19.25
49.78
k
rk hrk m
kr hkr ) + Sk
(Qrk + m
(13)
i=r
where , , Qrk and S are thermal conductivity, viscosity, interphase heat transfer according to Eqs. (14) and (18) and the
source term due to reactions heat, respectively.
2.3.1.
P
( h ) + (k k Uk hk ) = (k Tk ) + k uk k k
t k k k
t
2.4.1.
A new correlation was used to account interphase heat transfer between gas and liquid phases. The correlation covers the
wide range of operational conditions and uids physical properties at trickle ow regime with the following form (Heidari
and Hashemabadi, 2013):
Re 0.378 Pr 0.499
NuGL = 2.185
NuGL =
ReL
PrL
Eo0.627
hG,L dh
kG
(14)
(15)
Reaction kinetics
The last term in Eq. (8), Rk,i , stands for consumption or production of ith species due to chemical reactions. The following
reaction rate expressions were used to describe the HDS and
HDA reactions (Chowdhury et al., 2002):
Ar S + 2H2 Aromat + H2 S
2.4.2.
(9)
Poly-aromatics + H2 Di-aromatics
(10)
(11)
(12)
2.4.
In the current work, the non-isothermal conditions were evaluated for the reactor CFD model. The criteria for study a
packed bed at isothermal condition were reported by different researchers. Doraiswamy and Tajbl (1974) showed that the
practical reactor diameter-to-particles diameter ratio (dR /dp )
should be less than 4 for ignoring radial temperature. Carberry
(2001) stated that the maximum value for assumption of
isothermal temperature in the radial direction is dR /dp < 6.
In this work, the ratio of dR /dp based on catalysts equivalent diameter is about 13.6 (dR = 19 mm and dp = 1.4 mm) that
does not satisfy criteria of isothermal operation for the studied TBR. Furthermore, according to Carberry and White (1969)
the product yield in the packed bed reactors using 2D models is quite sensitive to temperature effects. Therefore, in the
current study, evaluation of temperature distribution in the
bed is necessary to achieve the best results for prediction of
reactor performance. The energy conservation equation for
each phase (gas, liquid and solid) based on EulerianEulerian
multiphase approach can be developed in the following form:
dh =
4
as (1 )
(16)
NuGS = (1 fe ) 0.111Re0.8
G PrG
1/3
NuLS = fe 0.111Re0.8
L PrL
2.4.3.
(17)
(18)
Heat transfer from the reactor wall to the bed at TBRs is significantly sensitive to the liquid ow rate. Based on experimental
data, Mariani et al. (2003) proposed the following correlation
to account wall to bed Nusselt number, Nuwall , for different
bed to particle diameter aspect ratios (4.7, 8.2, 17.2 and 34.3)
as
1/3
Nuwall = Re0.76
Lsu PrL
ReLsu =
ULc dp
L
(19)
(20)
3.
554
= 1+50,000C
HDS
RAr
HDA (polyaromatics)
HDA (diaromatics)
HDA (monoaromatics)
H2 S
in a tubular reactor with 500 mm length and 19 mm diameter, Fig. 1. The reactor consisted of two non-reactive zones at
two ends lled by inert particles with 0.2 mm average diameter. In the reactive zone, the trilobe catalysts (1.6 mm average
diameter and 3.5 mm average length) and inert spherical particles were mixed with ratio of 1:1.25 (vol/vol). In this study, the
equivalent diameter of particles was evaluated about 1.4 mm
on the basis of Sauter Mean Diameter (SMD) of trilobe catalysts. The more detail about effect of particles different size on
CFD model results of Chowdhury et al. (2002) reactor was presented by Gunjal and Ranade (2007). The thermal conductivity
of the solid phase on the basis of volumetric average of catalysts and inert particles thermal conductivity was evaluated
about 58 W/m K. The reactor wall temperature was controlled
by thermal system to prevent high increase in reactor temperature. Table 4 shows 18 different operational conditions used
at CFD simulations. The boundary conditions at the inlet zone
are equal with operational conditions, Table 4; furthermore,
67 000
66 462
133 024
199 203
555
LHSV (h1 )
P (MPa)
Temperature
sim-T1
sim-T2
sim-T3
sim-T4
573
593
613
653
4
4
4
4
2
2
2
2
200
200
200
200
0.014
0.014
0.014
0.014
Pressure
sim-P1
sim-P2
sim-P3
593
593
593
2
4
8
2
2
2
200
200
200
0.014
0.014
0.014
LHSV
sim-L1
sim-L2
sim-L3
593
593
593
4
4
4
1
2
4
200
200
200
0.014
0.014
0.014
sim-Q1
sim-Q2
sim-Q3
sim-Q4
593
593
593
593
4
4
4
4
2
2
2
2
100
200
300
500
0.014
0.014
0.014
0.014
sim-H2 S1
sim-H2 S2
sim-H2 S3
sim-H2 S4
593
593
593
593
4
4
4
4
2
2
2
2
200
200
200
200
0
0.014
0.03
0.08
Gas ow rate
Hydrogen
sulde
concentration
Cases
4.
4.1.
QG,NTP /QL
xvH
2S
isothermal bed. Fig. 2 depicts CFD simulations results in contrast with Chowdhury et al. (2002) experimental data. The
mean relative error of 5.5% between CFD and experimental
results (Chowdhury et al., 2002) was obtained which shows
that the developed CFD model can predict HDS reactor performance with appropriate accuracy.
4.2.
Mesh independency
4.3.
1
2
3
Cell
numbers
HDS reaction
conversion (%)
Run time
(h)
9000
22 000
88 000
40
42.6
42.7
10
45
115
556
Isothermal and
fully wetted
catalysts
(Chowdhury et
al., 2002)
Non-isothermal
and partially
wetted catalysts
2.5 1012
2.66 105
7.166 1012
4.23 105
8.5 102
1.33 103
6.04 102
9.62 102
4.4.
Fig. 3 shows HDS reaction conversion at different inlet temperatures (sim-T1, sim-T2, sim-T3 and sim-T4, Table 4). As it
can be inferred, the CFD simulation results show proper agreements with experimental data (Chowdhury et al., 2002). The
relative error between the experimental and optimized CFD
model with new reactions constants (Section 4.3) was found
about 1.8%. Therefore, it can be concluded that the modied
reactions kinetics can be used to study the effects of different
operational parameters on the performance and local properties of the HDS reactor, more accurately.
4.4.1.
Temperature distribution
4.5.
557
experimental data (Chowdhury et al., 2002) and CFD simulation results with 4.9% relative error. As it can be observed,
at constant gas and liquid ow rates, the reaction conversion
improves with an increase in the bed pressure. Enhancement
in the conversion rate can be caused by two reasons; rst,
when the operational pressure increases, the gas phase compresses and thus its velocity decreases through the bed. At
the same time, the momentum interaction between gas and
liquid phases causes the liquid velocity to reduce through the
bed, which, in turn, brings about increase in the liquid phase
residence time. Second, in the high reactor pressures, the
hydrogen concentration increases in the gas phase and therefore the hydrogen interphase mass transfer enhances which
gives rise to more conversion in the liquid phase reactants. As
a result, growth in the HDS conversion rate can be observed at
high operational pressures.
4.5.1.
4.6.
558
4.6.1.
Fig. 11 (A) Radial temperature distribution at z = 0.4 m and (B) contour of temperature in the sim-Q1 condition (Table 4).
4.7.
4.8.
559
560
In Fig. 14, distribution of average mass fraction of aromatic components is shown along the reactor length at
sim-H2S1 conditions. As observed, mass fractions of polyand di-aromatics components continuously decrease while
mono-aromatics mass fraction shows a maximum at the
inlet of the reactive zone. According to Eqs. (10)(12), HDAs
reactions kinetics are presented by a chain mechanism. In
the case of mono-aromatics reaction, due to high conversion of di-aromatics species respect to mono-aromatics, an
increase in the concentration of mono-aromatics components
occurs along the bed with a maximum point at z = 0.17 m.
After that, due to reduction in the di-aromatics concentration and consumption of mono-aromatics components, mass
fraction of mono-aromatics begins to decrease through the
reactor.
561
Fig. 16 Contour of the bed temperature: (A) with gasliquid interphase heat transfer and (B) without gasliquid interphase
heat transfer at sim-P3 conditions, Table 4.
4.9.
Gasliquid interphase heat transfer effect on
simulation results
In order to demonstrate gasliquid interphase coefcient
effect in the prediction of HDS reaction conversion and bed
temperature distribution, the CFD simulations at sim-P1,
sim-P2 and sim-P3 (Table 4) were repeated with eliminating
gasliquid interfacial heat transfer. As Fig. 15 shows, in the
case of no gasliquid heat transfer, Fig. 15A, the HDS conversion prediction is about 5% higher than non-isothermal
conditions. In effect, neglecting the heat transfer between gas
and liquid phases causes the reaction heat in the liquid phase
to only exchange with the solid phase. Thus, due to lower
heat loss in the liquid phase, the phase temperature increases
along the bed (Fig. 15B) which leads to the reaction conversion shows higher values than expected. In Fig. 16, contour of
temperature is shown with and without effect of gasliquid
interphase heat transfer during the CFD simulation at sim-P3.
As it can be inferred from the gure, neglecting the gasliquid
thermal interaction affects signicantly on the local temperature distribution, so that the location and values of hot spots
change in the bed. Subsequently, the entire phenomena such
as interphase mass transfer, phases properties and local reactants conversion are affected by difference at temperature
distribution. Therefore, it is safe to say that utilizing gasliquid
interphase heat transfer signicantly improves the accuracy of
TBR performance prediction.
5.
Conclusion
Acknowledgment
The authors would like to thank Pars Oil and Gas Company
(POGC - Islamic Republic of Iran) for the nancial support of
this work (Grant No. 91-203/TP).
562
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