Fuel Processing Technology 86 (16), 1761-1775 (2005)
Fuel Processing Technology 86 (16), 1761-1775 (2005)
Fuel Processing Technology 86 (16), 1761-1775 (2005)
www.elsevier.com/locate/fuproc
Abstract
A study on the improvement of the representative operating temperature from the temperature
profile of an industrial adiabatic reactor is presented. This temperature is used to simulate the reactor
performance by small scale laboratory isothermal reactors. An improved methodology for the
estimation of a Weighted Average Bed Temperature (WABT) was elaborated to simulate an industrial
multi-bed HDS reactor. The improved WABT, so called Weighted Average Reactor Temperature
(WART), was compared with the most usually used WABT in a wide range of operational conditions
as well as of kinetic parameters. In case of a multi-bed industrial hydrotreater, where quench zones
are located between the beds and the H2 flow rate, which enters each bed, is different, the optimal gas
to oil ratio was estimated for the laboratory-scale reactor.
D 2005 Elsevier B.V. All rights reserved.
Keywords: WABT; HDS reactor; HDS kinetics; Reactor simulation
* Corresponding author. Tel.: +30 210 772 3239; fax: +30 210 772 3155.
E-mail address: [email protected] (N.G. Papayannakos).
1
Present address: Laboratory for Petrochemical Engineering, Ghent University, Krijgslaan 281(S5), Ghent
B9000, Belgium.
0378-3820/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2005.04.002
1762
1. Introduction
The reliable simulation of the industrial hydrotreaters has become necessary as the
specifications on fuels quality will become stricter in the near future. After 2005, the
limitation of sulfur content in diesel will be approximately 50 ppm wt. [1] and the
accurate prediction of catalyst and reactor performance will be very crucial for the
product quality. A common way to simulate the performance of a commercial HDS
reactor is the conduction of kinetic experiments in a laboratory scale reactor using the
same catalyst, same operating conditions and a representative feed. To obtain
meaningful and ready to use data, it is necessary for the laboratory scale reactors to
fulfil some design criteria such as complete catalyst wetting, minimal backmixing
effects [27] and sufficient gasliquid mass transfer. Experiments are performed in a
wide range of the most critical parameters like reaction temperature and pressure,
WHSV and gas to oil ratio. The experimental data are treated with an appropriate model
so as to evaluate reaction kinetics, which is necessary for the simulation code of the
industrial reactors.
An unavoidable difference in operation between the industrial reactors and the
laboratory-scale ones is the catalyst bed temperature profile. In industrial reactors, the
adiabatic operation results in an increasing with length temperature profile while small
scale reactors operate isothermally. Consequently, it is practically difficult for the pilot
reactor to operate maintaining the same temperature profile with the industrial one.
Therefore, the kinetic experiments and the modelling of both reactors become
indispensable.
Another way to predict the performance of an industrial HDS reactor for a certain set of
operating conditions is the use of a Weighted Average Bed Temperature (WABT). All the
operational parameters of the laboratory-scale reactor like pressure and WHSV may be the
same as those of the industrial reactor while the isothermal temperature of the laboratoryscale reactor corresponds to the WABT of the industrial reactor. This method provides a
direct comparison of the performance of both reactors requiring only one experimental
point and bypassing the modelling codes. To the best of our knowledge, the literature that
concerns the estimation and use of the WABT is still limited [8], although this parameter is
an important and practical tool for a refinery engineer. It is not clear whether WABT is
applicable in a wide range of operational conditions as well as of kinetic parameters. It is
also unknown how the form of the temperature profile works on the WABT performance.
Moreover, in case of an industrial reactor which consists of two or even three catalytic
beds with intermediate quench zones, a key-parameter is the correct use of the feed gas to
liquid ratio in the laboratory-scale reactor. In addition, in multi-bed reactors the
temperature profile is not uniform as the gasliquid stream is cooled in quench zones
(Fig. 1).
The aim of this work is to investigate an improved model to predict a representative
Weighted Average Reactor Temperature (WART) applied in any single and multi-bed
hydrotreater. A theoretical comparison of the performance of adiabatic industrial HDS
reactors with isothermal laboratory-scale reactors is presented using as representative
temperature the widely used WABT and the proposed one (WART) with the improved
methodology.
1763
For the development of the WART equation it was considered that both reactors can be
characterised as ideal ones (plug flow, infinite solidliquidgas mass/heat transfer,
complete catalyst irrigation). First, because the high gas and liquid velocities of the
industrial reactor ensures total catalyst wetting and minimization of fluid flow dispersion
and second because the laboratory-scale reactor designed for scale up experiments should
be operated with bed dilution (in ascending or descending flow) to ensure plug flow for the
gas and liquid phases and total catalyst wetting. For the conditions examined in both
industrial and laboratory reactors, the gasliquid flow regime corresponds to trickle flow.
rHDS
1764
EHC
rHC
The model described below consists of the differential equations describing the mass
balances of sulfur, hydrogen sulphide, hydrogen consumption and hydrogen (Eqs. (3)(6))
as well as of the differential equation describing the heat balance in the adiabatic reactor
(Eq. (7)).
dCS
1
rHDS d
Moil
dmcat
dNH2 S
106
rHDS d
dmcat
M BH2 S
dHC
1
rHC d
dmcat
Moil
dNH2
1
rHC d
22:4
dmcat
dmcat
rHC d DH
The temperature at the beginning of the bed after a quench point (Tafter) is estimated
from the solution of the heat balance at the quench, which is:
Z
Tafter
Tbefore
Z
Moild Cpoil dT
Tafter
Tbefore
Z
NH2d CpH2 NH2 Sd CpH2 S dT
Tafter
Tbefore
NHQ2d CpH2 dT 0
9
The above equations are written considering that the gas at the inlet of a reactor as well
as the quench gas is pure hydrogen. For the specific heat capacity of the oil mixture
appearing in Eqs. (7) and (9), the following correlation is used [10].
Cpoil
0:415
p
4:1868d
0:0009d T 288:15
d15
1765
10
In this work, the heat balance equation in a quench zone was solved for N HQ2 choosing
such a temperature decrease in each quench zone so that the bed outlet temperature to be
within the practically acceptable limits.
WABT
Tin 2d T out
3
11
where Tin is the temperature at the reactor entrance and Tout is the outlet temperature. The
above equation takes the gradient of the temperature increase into account and is applied to
single bed reactors. In cases of reactors with more than one bed in series, the WABT put
into practice is estimated by the following weighted up expression:
n
X
WABT
WABT i d mcat;i
i1
n
X
12
mcat;i
i1
where the WABT is calculated by Eq. (9) for each bed and m cat,i is the catalytic mass of the
ith bed.
3.2. The improved WART model
In the event of an industrial reactor with more than one bed and intermediate quench
zones, one additional weighted up expression is needed, as the gas to oil ratio is different
1766
at the entrance of each bed. In case that the industrial reactor consists of three beds, the
required flow rate of H2 in the laboratory-scale reactor entrance (N HIR
) will be:
2
Q1
Q1
Q2
B1
B1
B1
IR
N
d
m
N
d
m
cat;1
cat;2
NH2
H2
H2
H2
H2
H2
H1 d mcat;3
13
IR
AR
Moil
mcat;1 mcat;2 mcat;3 Moil
where N HB2 1 is the molar flow rate of hydrogen at the inlet of the adiabatic reactor and
Q2
N HQ2 1, N H
are the molar flow rates of hydrogen in the quench zones before the second and
2
the third bed, respectively.
Replace of the reaction rate for hydrodesulfurization (Eq. (1)) into the differential mass
balance equation for the sulfur (Eq. (3)) and integration of the latter over the catalyst mass
for both an adiabatic, single bed reactor (Eq. (14)) and its equivalent, isothermal one (Eq.
(15)), yields correspondingly:
EHDS
Z Cout
Z mcat
S dC
kHDS d e Rd T d PH2
S
Moil d
dmcat
14
CSn
1 kH2 S d PH2 S
CSin
0
Z
Moil d
CSout
CSin
EHDS
dCS
RdT d
n kHDS d e
CS
mcat
0
PH2
dmcat
1 kH2 S d PH2 S
15
If Eq. (15) is applied to the isothermal reactor and Eq. (14) is applied to the adiabatic
one for the same conversion, the right-hand part of Eq. (14) can replace the left-hand part
of Eq. (15) to give:
EHDS
Z mcat
Z mcat
EHDS
PHIR2
e Rd T d PAR
H2
Rd Teq
e
d
dmcat
dmcat
16
1 kH2 S d PHIR2 S
1 KH2 S d PAR
0
0
H2 S
where the WART is defined as that temperature at which the operation of the isothermal
reactor would give the same sulfur conversion as the actual industrial reactor. Then, Eq.
(17) can be derived.
( Z
!
!)
E
Z mcat
AR
mcat e RdHDS
T dP
PHIR2
H2
WARTd Rd ln
dmcat ln
dmcat
1 kH2 S d PHIR2 S
1 kH2 S dPHAR2 S
0
0
EHDS
17
Due to the fact that the terms including the hydrogen and hydrogen sulphide partial
pressure in Eq. (17) are not sensitive to small variations of P H2 and P H2S, the above
equation can be recast into:
(
P
Z mcat
EHDS
PHAR
2
d
e Rd T dmcat
WARTd Rd ln
P
1 kH2 S dPHAR2 S 0
P
)
Z mcat
P HIR2
ln
dmcat
18
EHDS
P d
1 kH2 S d P HIR2 S 0
where P HAR
, P HAR
, P HIR2, P HIR2S are the average pressures of hydrogen and hydrogen sulphide
2
2S
in the adiabatic and the isothermal reactor respectively.
1767
WARTd Rd ln
EHDS
Rd T
dmcat
lnmcat
19
EHDS
Eq. (19) can be applied in cases of one but also of two or more beds in sequence
separated by one or more quench zones respectively. Consequently, the proposed equation
for the evaluation of the WART is:
(
!
!)
Z mcat;i E
nX
nX
BED
BED
HDS
Rd
T
WARTd Rd ln
e cat dmcat ln
mcat;i EHDS ; nBED z2
0
i1
i1
20
Eq. (20) can be written in terms of bed length:
!
(
!)
Z Li E
nX
nX
BED
BED
HDS
Rd
T
WARTd Rd ln
qB;i SR;i
e
dx ln
mcat;i
EHDS
0
i1
21
i1
Temperature (K)
620
QUENCH B
QUENCH A
625
615
610
605
L1 = 2.64
L 2 = 5.66
L 3 = 8.17
600
0
10
15
20
1768
621.0
+ 0.2 K
WART (K)
620.8
620.6
620.4
- 0.2 K
620.2
620.0
50
70
90
110
130
150
170
190
EHDS (kJ/mol)
Fig. 3. The equivalent temperature of isothermal reactor vs. the activation energy of HDS reactions (three bed
reactor).
values of E HDS and given in Fig. 3. It is obvious that there is a very slight influence of the
activation energy (E HDS) on the WART. Four times higher activation energy (from 50 to
200 kJ/mol) gives 0.4 K difference on the WART. Therefore, if a typical value of E HDS is
used (100 kJ/mol), Eq. (21) can be simplified in the following form:
WART
ln
nX
BED
i1
12000
!
Z Li
12000
T
qB;i SR;i
e
dx ln M tot
22
The inlet hydrogen flow rate in an isothermal reactor for the simulation of a multi-bed
adiabatic reactor is estimated by Eq. (13), given before. A similar approach has been used
in a recent work [11] mainly concerning single bed reactors, neglecting the correction of
the gas/oil ratio from the quench streams and recommending more than five
thermocouples for reliable results even for one bed reactor. Experimental evidence of
the superiority of this approach is given for cases with one-bed reactor.
4. Discussion of results
In this section, the set of the four mass balances describing the isothermal reactor model
is solved using both the existing WABT and the improved WART and the results are
compared with those calculated from the solution of the equations of the non-isothermal
1769
20
15
Error (%) 10
5
0
2.5
WHSV (h )
Tin (K)
601
2.1
-1
1.7
0.9
1.3
0.5
573
587
615
Fig. 4. Variation of the WABT error with WHSV and T in for E HC = 13 kJ/mol.
model (Eqs. (3)(7)) in case of a three bed reactor, as it is considered the most complicated
reactor configuration. The procedure was the following. For a given set of kinetic
equations the temperature profile of the adiabatic reactor was calculated. Then, the WABT
and WART were obtained. These temperature values were used to solve the isothermal
reactor model and finally calculate the exit sulfur concentration in each case. A wide range
of kinetic and operating parameters have been tested considering the hydrotreatment of a
feed ranging from heavy gas oil to diesel oil with a typical 1.4 wt.% sulfur content and
total reactor pressure 5.4 MPa. The choice of the range of the kinetic parameters was based
on the variation of the sulfur conversion which was in the range from 20% to 99.99%.
72
54
Error (%) 36
18
0
2.5
601
2.1
WHSV (h )
1.7
0.9
-1
1.3
0.5
573
587
Tin (K)
615
Fig. 5. Variation of the WABT error with WHSV and T in for E HC = 5 kJ/mol.
1770
Table 1
The values of the kinetic parameters in the case of a three beds reactor
Kinetic parameters
Three beds
2.4 d 106
127
2.8 d 10 3
2.5
0.12
1.1
1500
23
where: C Sest is the remaining sulfur concentration at the outlet of the adiabatic reactor, as it
is calculated from the solution of the non-isothermal model and C Spred is the remaining
sulfur concentration at the outlet of the reactor, as it is calculated from the solution of the
isothermal model, using either the WABT or the improved WART.
4.1. Three bed reactor
The assessment of the already existing WABT starts by comparing its performance at
two different E HC. In Fig. 4, the WABT error is presented versus WHSV and Tin in case
that E HC = 13 kJ/mol. In Fig. 5, the same procedure is followed for E HC = 5 kJ/mol. For
both runs, the gas to oil ratio (Q/L) was 290 Nm3/m3 and the values of the other kinetic
parameters are presented in Table 1. When higher hydrogen consumption rate occurs and a
steeper temperature profile is developed (Fig. 6), the error from the use of the existing
WABT becomes quite high (up to 62% for E HC = 5 kJ/mol, against 18% when E HC = 13 kJ/
670
T (K)
660
650
640
EHC = 13 kJ/mol
EHC = 5 kJ/mol
630
620
0
20
40
60
80
100
% Reactor Length
Fig. 6. Temperature profile in the three-bed adiabatic reactor for two E HC values.
1771
35
30
Error (%)
25
20
15
10
5
0
5
11
13
EHC (kJ/mol)
Fig. 7. Variation of the WABT error with E HC.
mol). In Fig. 7, the descending line of the WABT error with increasing E HC is presented.
The results of Fig. 7 are given for WHSV = 1 h 1, Q/L = 290 Nm3/m3 and Tin = 623 K. The
values of the other kinetic parameters are given in Table 1.
Fig. 8 is the respective figure to Fig. 5, where the improved WART is tested for the
same values of the operating conditions as well as of the kinetic parameters. The results
show that the error values from the use of the improved WART are lower than 11%
whereas the respective ones using the existing WABT mode are up to 62%.
In Fig. 9, the error variation versus E HC is presented using the same parametric and
operating values as in Fig. 7. The comparison of the two plots indicates that for the same
range of E HC (513 kJ/mol), the error in case of the WABT varies from 4.8% to 28.9%
whereas the errors resulting from the use of WART are between 4.8% and 6.6%. It should
be mentioned that the values for the operating parameters have been chosen so that the two
WABT alternatives are assessed in occasion of deep hydrodesulfurization. The 28.9% error
12
Error (%) 6
3
0
2.5
601
2.1
WHSV (h )
1.7
0.9
-1
1.3
0.5
573
587
Tin (K)
615
Fig. 8. Variation of the WART error with WHSV and T in for E HC = 5 kJ/mol.
1772
7
6
Error (%)
5
4
3
2
1
0
5
11
13
EHC (kJ/mol)
Fig. 9. Variation of the WART error with E HC.
corresponds to 65 ppm outlet sulfur concentration and the 4.8% error corresponds to 235
ppm outlet sulfur concentration.
In Fig. 10, the performance of the proposed WART is evaluated in relation with WHSV
(0.52.5 h 1) and Q/L (200800 Nm3/m3) variation. It is observed that all the errors are
lower than 8%. The error values are presented for Tin = 603 K and for the kinetic
parameters given in Table 1.
Finally, in Figs. 11 and 12 the assessment of the WART is realised with respect to the
kinetic parameters. More specifically, in Fig. 11, the WART error variation with E HDS (84
146 kJ/mol) is presented when k HDS varies from 2.8 d 103 to 8.3 d 106 kgoil ppm1n /s
kgcat MPaH2. In Fig. 12 the WART performance is assessed in relation with E HDS (84146
kJ/mol) for three different reaction orders (n = 1, 1.5, 2) with k HDS = 2.8 d 103 kgoil
ppm1n /s kgcat MPaH 2.
10
7.5
Error (%) 5
2.5
200
Q/L (Nm3/m3)
800
2.5
2.1
WHSV (h-1)
1.7
0.9
600
1.3
0.5
400
Fig. 10. Variation of the WART error with WHSV and Q/L.
K HDS
10
kg oil ppm 1n
S
Error (%)
1773
2.8e3
s kg cat MPa H
2
1.4e5
1.4e6
8.3e6
0
80
90
100
110
120
130
140
150
EHDS (kJ/mol)
Fig. 11. Variation of the WART error with E HDS and k HDS.
In both cases the values of the operating parameters were considered to be Tin = 603 K,
WHSV = 1 h 1, Q/L = 290 Nm3/m3 and the values of the other kinetic parameters were
those of Table 1. It is remarked that the error values are always lower than 8.5%.
5. Conclusions
In this work, a comparison between the most commonly used WABT and an improved
WABT, so called WART is performed. It should be pointed out that the use of WART
needs three known temperature points in an industrial bed (inlet, middle and outlet),
12
Error (%)
10
8
n = 1.0
n = 1.5
n = 2.0
6
4
2
0
80
90
100
110
120
130
140
EHDS (kJ/mol)
Fig. 12. Variation of the WART error with E HDS and n.
150
1774
whereas the existing WABT needs two temperature points (inlet and outlet). The analysis
of the results that was set forth for one-, two- and three-bed reactors showed that the use of
the WABT is not authoritative. It may lead either to good or very bad results especially in
cases of deep desulfurization. On the contrary, the employment of the improved WART
always leads to good predictions. Remark that only results for the three-bed case are
presented in this paper since similar trends were obtained when the analysis was applied to
the one-or two-bed cases. The appreciation of the WART was realised in a wide range of
operating and kinetic parameters and the calculated error in exit sulfur concentration was
always lower than 12%.
Symbols
C
concentration (ppm wt.)
CH specific hydrogen consumption (Nm3 H2/kgoil)
CHT maximum specific hydrogen consumption (Nm3 H2/kgoil)
Cp
specific heat capacity (kJ/kg/K for oil, kJ/kmol/K for H2 and H2S)
d 15 oil density at 288 K (g/ml)
E
activation energy (kJ/mol)
k H2S inhibiting factor (MPa 1)
k HC frequency factor of HC reaction constant (kg2oil/s d kgcat d MPaH2 d Nm3H2)
k HDS frequency factor of HDS reaction constant (kgoil d ppm1n
/s d kgcat d MPaH2)
s
Li
length of ith catalytic bed (m)
MB molecular weight (g/mol)
m cat mass of catalyst (kg)
M oil mass flowrate of oil (kg/s)
M tot total mass of catalyst for all beds (kg)
N
molar rate (mol/s)
n
reaction order
n BED number of beds
P
partial pressure (MPa)
Q/L gas to oil ratio (Nm3/m3)
r
apparent reaction rate
R
ideal gas constant (8.314 J/mol/K)
SR
cross section area of catalytic bed (m2)
T
temperature (K)
WABT weighted average bed temperature (K)
WART weighted average reactor temperature (K)
WHSV weight hourly space velocity (h 1)
Greek Symbols
DH exotherm of reactions (kJ/Nm3 H2)
qB
catalytic bed bulk density (kg/m3)
Subscripts and superscripts
after after the quench point
1775
AR adiabatic reactor
B
adiabatic bed
before before the quench point
HC reaction of H2 consumption
HDS hydrodesulfurization reaction
i
index number
in
inlet
out outlet
IR
isothermal reactor
Q
quench
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