Ind. Eng. Chem. Res.

1996, 35, 3311-3318 3311

Hydrodesulfurization of Dibenzothiophene on a CoMo/Al2O3

Catalyst: Reaction Network and Kinetics
Valérie Vanrysselberghe and Gilbert F. Froment*
Laboratorium voor Petrochemische Techniek, Rijksuniversiteit Gent, Krijgslaan 281, B-9000 Gent, Belgium

The hydrodesulfurization of dibenzothiophene on a commercial CoMo/Al2O3 catalyst was studied

in a multiphase reactor. The operating conditions were varied over the following range:
temperatures, 513-573 K; total pressures, 50-80 bar; molar hydrogen to hydrocarbon ratios,
1.1-4.1. Hougen-Watson rate equations for the hydrogenolysis of dibenzothiophene into
biphenyl and H2S, for the hydrogenation of dibenzothiophene into tetra- and hexahydrodiben-
zothiophene, for the hydrogenation of biphenyl into cyclohexylbenzene, and for the subsequent
hydrogenation of cyclohexylbenzene into bicyclohexyl were developed. Two different types of
active sites were considered: σ sites for hydrogenolysis and τ sites for hydrogenation. The surface
reaction between adsorbed reactants and two competitively adsorbed hydrogen atoms was found
to be the rate-determining step for both types of reaction.

Introduction
Thiophenic components are known to be the most
refractory organic sulfur-containing components. Rigor-
ous kinetics for the hydrodesulfurization (HDS) of
thiophene and benzothiophene have already been de-
rived (Van Parys and Froment, 1986; Van Parys et al.,
1986). For dibenzothiophene, hydrodesulfurization rate
equations have been reported by Broderick and Gates
(1981) and recently by Edvinsson and Irandoust (1993).
Broderick and Gates (1981) neglected the hydrogenation
of biphenyl into cyclohexylbenzene, while Edvinsson and
Irandoust (1993) did not determine the influence of the
H2S concentration on the reaction rates. Furthermore,
cyclohexylbenzene and bicyclohexyl were lumped, so
that no rate equation was developed for the hydrogena-
tion of cyclohexylbenzene into bicyclohexyl. The present
study is part of a wider effort aiming at a more rigorous
kinetic modeling of the hydrodesulfurization of oil
fractions introduced by Froment et al. (1994) and in
which the kinetics of HDS of substituted thiophenes,
benzothiophenes, and dibenzothiophenes are related to
those of the unsubstituted components through elec-
tronic and steric factors. The purpose of this paper is
to develop rate equations for all reactions in the network
for the hydrodesulfurization of dibenzothiophene on a
commercial CoMo/Al2O3 catalyst under operating condi-
tions relevant to industrial applications.

Experimental Setup
A flow scheme of the experimental setup is shown in
Figure 1. The liquid hydrocarbon was fed into the
reactor with a high-pressure pump (Spectra-Physics
P1000) (1). The hydrocarbon feed was metered with a
Sartörius electrobalance type BA 4100 (2). The hydro-
gen, the hydrogen sulfide, the nitrogen, and the meth-
ane feed were controlled and measured with a set of
electronic mass flow controllers of the type Brooks 5850
TR (3). Hydrogen sulfide and nitrogen were used in the
pretreatment of the catalyst. Methane was used as
internal standard for the on-line analysis of the reactor
effluent. The gases and the liquid feed were preheated
(4) and mixed (5) before entering the reactor (6). The
effluent section was also heated to avoid condensation.
The reaction was carried out in a multiphase Robinson-
Mahoney reactor. Complete mixing in this reactor was
verified by residence time distribution studies. Visual
S0888-5885(96)00099-1 CCC: $12.00
Figure 1. Experimental setup.
observations in a glass vessel showed the gas to be
perfectly distributed over the liquid phase (Yu and
Froment, unpublished). The reactor is made of stainless
steel and can operate at pressures up to 140 bar and at
temperatures up to 350 °C. The temperature was
measured by means of thermocouples and controlled by
a PID temperature controller. The pressure was con-
trolled by a back pressure regulator (7). The effluent
of the reactor consisted of gas and liquid phases at high
pressure and high temperature. Both phases were
separated by means of a cyclone (8). The liquid was
collected in the liquid holder (9). The gas product
stream entered a mist eliminator (10) to recuperate
entrained liquid droplets that were added to the already
recuperated liquid phase. The cyclone, the liquid holder,
and the demister were kept at the same pressure and
© 1996 American Chemical Society
3312 Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996
temperature as in the reactor to avoid changes in
composition of both phases. A small fraction of the gas
phase was taken for on-line gas chromatographic (GC)
(11) analysis. The remaining gas phase was cooled (12),
so as to condense heavy fractions and then was scrubbed
by means of a sodium hydroxide solution (13) to remove
hydrogen sulfide. The liquid product was cooled (14)
and flashed (15) under ambient conditions. The light
gases, dissolved in the liquid phase, were partially
desorbed and collected in a gas buret (16). The flow
rates and compositions of the desorbed gas mixture and
the liquid product were measured and analyzed off-line
by means of the GC. The GC contained a TCD detector,
a Hayesep D packed column, and a backflush column
OV-101 to analyze light gases such as hydrogen, hy-
drogen sulfide, and methane. The GC also contained a
FID detector and a capillary column HP-5 for the
analysis of the hydrocarbons.
Procedure
Experiments were performed using a solution of 2 wt
% dibenzothiophene (DBT) (0.35 wt % sulfur) dissolved
in Parapur (FINA). Parapur is a paraffinic mixture
containing 5.23 wt % n-decane, 48.42 wt % n-undecane,
33.64 wt % n-dodecane, 12.52 wt % n-tridecane, and 0.19
wt % n-tetradecane. Experiments were carried out at
total pressures between 50 and 80 bar and at temper-
atures between 513 and 573 K. The molar flow rate
F0DBT was varied between 1.74 × 10-6 and 4.04 × 10-6
kmol/h and the molar hydrogen to hydrocarbon ratio,
γ, between 1.1 and 4.1. The molar hydrogen to methane
ratio was kept constant at 6.4 for all experiments, except
for some experiments at 70 bar where the molar
hydrogen to methane ratio was kept constant at 7.0. The
total number of experiments amounted to 98.
The catalyst used was the commercial HDS catalyst
AKZO Ketjenfine 742 containing 5-30 wt % MoO3,
1-10 wt % CoO, 0-6 wt % SiO2, and 0-10 wt % P2O5
on an alumina support and with a surface area of 264
mcat2/gcat and a pore volume of 0.52 cm3/gcat. It was
crushed to a size between 710 and 800 µm to avoid
diffusional limitations, and 2.53 gcat was diluted with
nonporous inert alumina. Diffusional limitations were
calculated using the Weisz-Prater criterium. In addi-
tion, it was shown experimentally that no diffusional
limitations exist with 0.71-0.80 mm particles. Experi-
ments with 1.2 mm particles as well as with 0.63-0.90
mm particles gave identical values for the reaction rates
for given conditions. The catalyst was dried at 423 K
in the reactor by means of nitrogen and was then heated
to 623 K, still under nitrogen. It was pretreated by a
15 vol % mixture of H2S in H2 during 6 h at 1 bar and
623 K. The gas flow rate was 10 L(STP)/h. The catalyst
was cooled under nitrogen. It was then stabilized with
the liquid feed at T ) 533 K, pt ) 50 bar, F0DBT ) 1.97
× 10-6 kmol/h, γ ) 4.1, and H2/CH4 ) 6.4. The stability
of the catalyst activity and selectivity was frequently
checked by performing experiments at reference operat-
ing conditions. Catalyst deactivation and hydrocracking
of the solvent Parapur did not occur under the condi-
tions mentioned above.
Discussion of the Results
The reaction products of the HDS of DBT were
biphenyl (BPH), cyclohexylbenzene (CHB), bicyclohexyl
(BCH), and H2S. Tetra- (THDBT) and hexahydrodiben-
zothiophene (HHDBT) were not detected.
0 g
Figure 2. Conversions as a function of W/(FDBT - FDBT ): (b)
total conversion of DBT, (9) conversion of DBT into BPH, (2)
conversion of DBT into CHB. Experimental conditions: T ) 553
K, pt ) 60 bar, H2/CH4 ) 6.39, and H2/HC ) 1.10.
The catalytic reactions only take place in the com-
pletely wetted catalyst. Consequently, the fraction of
DBT that evaporated, FgDBT, is excluded from the con-
tact with the catalyst surface and does not participate
in the reactions. For a given molar feed rate, F0DBT, the
molar flow rate of DBT in contact with the active sites
is F0DBT - FgDBT. Consequently, the space time is de-
fined as W/(F0DBT - FgDBT) and the conversion xDBT of
DBT as well as its conversion xBPH into BPH, xCHB into
CHB, and xBCH into BCH are defined as:
0 g l
FDBT - FDBT - FDBT
xDBT ) 0 g
FDBT - FDBT
g l
FBPH + FBPH
xBPH ) 0 g
FDBT - FDBT
FgCHB + FlCHB
xCHB ) 0 g
FDBT - FDBT
FgBCH + FlBCH
xBCH ) 0 g
FDBT - FDBT
The DBT total conversion varied from 12.3 to 87.0%,
depending on the operating conditions. As expected, the
conversions xDBT, xBPH, xCHB, and xBCH increased with
temperature. DBT was mainly desulfurized into BPH
and H2S. It was also hydrogenated into THDBT and/
or HHDBT. Since these partially hydrogenated DBTs
were not detected, they are highly reactive intermedi-
ates that are instantaneously converted into CHB and
H2S. BPH was further hydrogenated into CHB. Com-
plete hydrogenation of BPH only occurred at 573 K and
led to very small amounts of BCH. Typical sets of
conversion vs spacetime plots are shown in Figures 2
and 3.
The dependence of the conversions xDBT, xBPH, and
xCHB on γ is given in Figure 4 for a given value of W/
(F0DBT - FgDBT), T, pt, and H2/CH4. The dependence of
the selectivity for hydrogenation defined by the ratio
xCHB/xDBT and of the H2S liquid concentration CH2S on γ

Figure 3. Total conversion of DBT as a function of W/(FDBT 0
- 1275 kgcat h kmol-1, H2/CH4 ) 6.39, and H2/HC ) 4.13.
g
FDBT ) at various temperatures: (b) 513, (9) 533, (2) 553, and (O)
573 K. Experimental conditions: pt ) 80 bar, H2/CH4 ) 6.38, and
H2/HC ) 1.33.
Figure 4. Conversions as a function of H2/HC: (b) total conver-
sion of DBT, (9) conversion of DBT into BPH, (2) conversion of
DBT into CHB. Experimental conditions: T ) 533 K, pt ) 70 bar,
0 g
W/(FDBT - FDBT ) ) 1029 kgcat h kmol-1, and H2/CH4 ) 7.02.
Figure 5. Selectivity for hydrogenation, xCHB/xDBT, and H2S liquid
concentration, CH2S, as a function of H2/HC. Experimental condi-
0 g
tions: T ) 533 K, pt ) 70 bar, W/(FDBT - FDBT ) ) 1029 kgcat h
kmol , and H2/CH4 ) 7.02.
-1
is shown in Figure 5. A higher γ resulted in higher
conversions. Furthermore, H2S increased the selectivity
for hydrogenation, indicating a different effect of H2S
Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996 3313
Figure 6. Selectivity for hydrogenation, xCHB/xDBT, and conver-
sions as a function of total pressure, pt,: (b) total conversion of
DBT, (9) conversion of DBT into BPH, (2) conversion of DBT into
0 g
CHB. Experimental conditions: T ) 553 K, W/(FDBT - FDBT ))
upon hydrogenation and hydrogenolysis (Van Parys and
Froment, 1986; Van Parys et al., 1986; Edvinsson and
Irandoust, 1993).
The dependence of xDBT, xBPH, and xCHB and of the
selectivity for hydrogenation xCHB/xDBT on the total
pressure, pt, is shown in Figure 6 for a given value of
W/(F0DBT - FgDBT), T, γ, and H2/CH4. Within the range
of 50-80 bar, xDBT, xBPH, and xCHB increased with the
total pressure. The selectivity for hydrogenation reac-
tions was favored by higher total pressures.
Kinetic Analysis
Reaction Scheme. The following reaction network
for the HDS of DBT into BPH, CHB, BCH, and H2S is
deduced from the experimental program:
S
rDBT,τ rDBT,σ
+ H2S
S S
rBPH,τ
+ H2S
rCHB,τ
The hydrogenolysis reactions and the hydrogenation
reactions are considered to take place on different kinds
of active sites, σ and τ. The existence of two different
types of active sites has already been pointed out by
Delmon (1979), Gates et al. (1979), Broderick and Gates
(1981), Vrinat (1983), Van Parys and Froment (1986),
Van Parys et al. (1986), and Edvinsson and Irandoust
(1993).
Parameter Estimation. The experiments were
performed in a perfectly mixed flow reactor. The
differential method of kinetic analysis was applied
(Froment and Bischoff, 1990). The net production rates,
3314 Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996

Ri, derived from the above reaction scheme, are defined When the calculated value Fadeq exceeds the tabulated
as R-percentage point of the F-distribution with nv - p -
∑(ns - 1)v and ∑(ns - 1)v degrees of freedom, there is
RBPH ) rDBT,σ - rBPH,τ a probability of 1 - R that the model is inadequate and
the model is rejected. The significance of the individual
parameters is tested by means of their calculated
RCHB ) rDBT,τ + rBPH,τ - rCHB,τ t-values. The significance of the overall regression is
evaluated by means of the F-value, defined by Froment
RBCH ) rCHB,τ and Bischoff (1990)

The total rate of disappearance of DBT is given by h)v k)v i)n

∑ ∑ σhk∑ R̂ihR̂ik/p
RDBT ) rDBT,σ + rDBT,τ h)1 k)1 i)1
Fregr )
h)v k)v i)n
Experimental values for Ri were directly obtained from
the experimental conversions xi:
∑∑ ∑
h)1 k)1
i)1
σhk
(Rih - R̂ih)(Rik - R̂ik)/(nv - p)

xi When the calculated Fregr value exceeds the tabulated

Ri ) 0 g
W/(FDBT - FDBT )
Several plausible reaction mechanisms and correspond-
ing Hougen-Watson rate equations were derived. The
various reaction mechanisms only differ by the way of
adsorption of hydrogen: atomically (A) or molecularly
(M); competitively in hydrogenolysis (σc) and hydroge-
nation (τc); noncompetitively on a third type of active
sites (σnc, τnc); noncompetitively on the active sites for
hydrogenation (στ) or hydrogenolysis (τσ). For the
adsorption of atomic hydrogen, the addition of the first
H atom, the addition of the second H atom, and the
simultaneous addition of two hydrogen atoms were
R percentage point of the F distribution with degrees of
freedom (p, nv - p), the regression is considered to be
meaningful. Among the rival models, the one with the
highest Fregr value is considered the best. However, the
parameters have to satisfy physicochemical laws. The
adsorption equilibrium constants have to obey the van’t
Hoff temperature dependence; the rate coefficients have
to obey the Arrhenius temperature dependence. Con-
straints on the adsorption entropies were derived by
Boudart et al. (1967).
For the estimation of the parameters, the following
reparametrization of the rate coefficients and the ad-
sorption equilibrium constants was carried out:

[ ( )]
considered. Reaction with H2 directly from the liquid
phase was also considered (σER, τER). Ea 1 1
ki,s ) A# exp -
Rgas T Tm
-
The sulfur atom of DBT, THDBT, or HHDBT remains

[ ( )]
on the catalyst surface after reaction. Its removal
occurs via reaction with H2 directly from the liquid #
∆H0a 1 1
phase (SER) or via a mechanism corresponding with the Ki,s ) A exp -
Rgas T Tm
-
mechanism of hydrogenolysis on the σ sites (Sσ, Sτ, Snc).
Either the adsorption of the reactants or the surface
reaction between the adsorbed species or the desorption Tm is the average temperature of the experiments, here
of the reaction products on both active sites σ and τ could 540 K. The discrimination between the rival models
be the rate-determining step (rds). The discrimination was based on statistical tests and physicochemical
involved 174 rival models. criteria. The discrimination and parameter estimation
The parameters were obtained by minimization of the led to the reaction mechanism AσcτcSσ: (a) hydrogenoly-
following multiresponse objective function S(θ) by means sis of DBT into BPH and H2S on the σ sites
of a Marquardt routine:
DBT + σ h DBT.σ
h)v k)v i)n

∑ ∑ σhk∑(Rih - R̂ih)(Rik - R̂ik) f min

θ
S(θ) )
h)1 k)1 i)1
H2 + 2σ h 2H.σ
The experimental program contained a number of
replicated experiments so that the “pure error” sum of
squares could be calculated and the model adequacy DBT.σ + 2H.σ f BPH.σ + S.σ + σ (rds)
could be tested by means of the following F-test (Fro-
ment and Bischoff, 1990):
S.σ + 2H.σ h H2S.σ + 2σ
lack of fit sum of squares
s)r
nv - p - ∑(ns - 1)v
s)1
BPH.σ h BPH + σ

Fadeq )
pure error sum of squares H2S.σ h H2S + σ
s)r

∑(ns - 1)v
s)1
(b) hydrogenation of DBT into THDBT and HHDBT on
the τ sites, followed by hydrogenolysis into CHB and

H2S on the σ sites
DBT + τ h DBT.τ
H2 + 2τ h 2H.τ
DBT.τ + 2H.τ h DHDBT.τ + 2τ
DHDBT.τ + 2H.τ h THDBT.τ + 2τ
THDBT.τ h THDBT + τ
Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996 3315
kBPH,τKH,τKBPH,τCBPHCH2
rBPH,τ )
(1 + KDBT,τCDBT + xKH,τCH2 + KBPH,τCBPH)3
kCHB,τKH,τKCHB,τCCHBCH2
rCHB,τ )
(rds) (1 + KDBT,τCDBT + xKH,τCH2 + KBPH,τCBPH)3
with

THDBT.τ + 2H.τ h HHDBT.τ + 2τ KDBT,σ ) 7.56868 × 101 (m3/kmol)

HHDBT.τ h HHDBT + τ

THDBT + σ h THDBT.σ
KH,σ ) 3.36312 × 10-11 exp
[ 113232
RgasT ] (m3/kmol)

[ ]
HHDBT + σ h HHDBT.σ
48214
KBPH,σ ) 3.84984 × 10-4 exp (m3/kmol)
H2 + 2σ h 2H.σ RgasT

[ ]
THDBT.σ + 2H.σ f PHCH.σ + S.σ + σ
105670
KH2S,σ ) 1.47118 × 10-8 exp
PHCH.σ + 2H.σ h CHB.σ + 2σ RgasT
(m3/kmol)
HHDBT.σ + 2H.σ f CHB.σ + S.σ + σ

[ ]
S.σ + 2H.σ h H2S.σ + 2σ 122770
kDBT,σ ) 2.44336 × 1010 exp -
RgasT
CHB.σ h CHB + σ
(kmol kgcat-1 h-1)
H2S.σ h H2S + σ

(c) hydrogenation of BPH into CHB on the τ sites

BPH + τ h BPH.τ
KDBT,τ ) 2.50395 × 10-7 exp
[76840
RgasT ] (m3/kmol)

[ ]
H2 + 2τ h 2H.τ
142693
KH,τ ) 1.40255 × 10-15 exp (m3/kmol)
RgasT
BPH.τ + 2H.τ f PHCHD.τ + 2τ (rds)

[ ]
PHCHD.τ + 2H.τ h PHCH.τ + 2τ
37899
KBPH,τ ) 4.96685 × 10-4 exp (m3/kmol)
PHCH.τ + 2H.τ h CHB.τ + 2τ RgasT

CHB.τ h CHB + τ
(d) hydrogenation of CHB into BCH on the τ sites kDBT,τ ) 2.86757 × 1016 exp -
[ 186190
RgasT ]
CHB + τ h CHB.τ (kmol kgcat-1 h-1)
H2 + 2τ h 2H.τ

CHB.τ + 2H.τ f CHCHD.τ + 2τ (rds) kBPH,τ ) 3.41120 × 1023 exp -

[ 255714
RgasT ]
CHCHD.τ + 2H.τ h CHCH.τ + 2τ (kmol kgcat-1 h-1)

CHCH.τ + 2H.τ h BCH.τ + 2τ

kCHB,τKCHB,τ (573 K) ) 3.38631 × 10-1
BCH.τ h BCH + τ (m3 kgcat-1 h-1)
The corresponding rate expressions are given by
The parameter estimates, their corresponding 95%
rDBT,σ ) confidence intervals, the calculated t-values, the calcu-
kDBT,σKH,σKDBT,σCDBTCH2 lated Fregr value, and Fadeq value are shown in Table
1. The selected model was found to be statistically
(1 + KDBT,σCDBT + xKH,σCH2 + KBPH,σCBPH + KH2S,σCH2S)3
adequate. The regression was found to be significant
and all parameters were statistically significant. The
kDBT,τKH,τKDBT,τCDBTCH2 temperature dependence of KDBT,σ was statistically
rDBT,τ ) nonsignificant. The physicochemical rules for the
(1 + KDBT,τCDBT + xKH,τCH2 + KBPH,τCBPH)3 activation energies, Ea, for the adsorption enthalpies
3316 Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996

Table 1. Parameter Estimates, 95% Confidence Intervals, t Values, Fregr Value, and Fadeq Valuea
parameter estimate lower limit upper limit t value
KDBT,σ 7.56868 × 101 7.35331 × 101 7.78405 × 101 7.02849 × 101
KBPH,σ A# 1.79037 × 101 1.39478 × 101 2.18595 × 101 9.05173
∆H -4.82140 × 104 -5.55333 × 104 -4.08947 × 104 -1.31744 × 101
KH,σ A# 3.07994 1.68108 4.47880 4.40349
∆H -1.13232 × 105 -1.22443 × 105 -1.04020 × 105 -2.45847 × 101
KH2S,σ A# 2.49703 × 102 2.32196 × 102 2.67210 × 102 2.85260 × 101
∆H -1.05670 × 105 -1.10430 × 105 -1.00910 × 105 -4.44026 × 101
kDBT,σ A# 3.18252 × 10-2 1.97179 × 10-2 4.39326 × 10-2 5.25719
Ea 1.22770 × 105 1.15508 × 105 1.30032 × 105 3.38130 × 101
KDBT,τ A# 6.87701 6.87182 6.88220 2.64876 × 103
∆H -7.68399 × 104 -8.87463 × 104 -6.49335 × 104 -1.29074 × 101
KBPH,τ A# 2.31738 2.31659 2.31816 5.89640 × 103
∆H -3.78986 × 104 -4.60500 × 104 -2.97473 × 104 -9.29873
KH,τ A# 9.13800 × 10-2 8.95236 × 10-2 9.32364 × 10-2 9.84469 × 101
∆H -1.42693 × 105 -1.56505 × 105 -1.28881 × 105 -2.06625 × 101
kDBT,τ A# 2.70832 × 10-2 2.48567 × 10-2 2.93098 × 10-2 2.43274 × 101
Ea 1.86190 × 105 1.76425 × 105 1.95955 × 105 3.81358 × 101
kBPH,τ A# 5.99185 × 10-2 1.12721 × 10-2 1.08565 × 10-1 2.46343
Ea 2.55714 × 105 2.48667 × 105 2.62761 × 105 7.25727 × 101
kCHB,τKCHB,τ (573 K) 3.38631 × 10-1 3.33916 × 10-1 3.43345 × 10-1 1.43647 × 102
a Fregr value ) 20366; Fadeq value ) 1.30.

Table 2. Adsorption Equilibrium Constants and Rate

Coefficients at 573 K
KDBT,σ ) 7.56868 × 101 m3/kmol
KH,σ ) 7.01679 × 10-1 m3/kmol
KH2S,σ ) 6.27912 × 101 m3/kmol
KBPH,σ ) 9.53728 m3/kmol
kDBT,σ ) 1.58251 × 10-1 kmol/(kgcat h)
KDBT,τ ) 2.52021 m3/kmol
KH,τ ) 1.41658 × 10-2 m3/kmol
KBPH,τ ) 1.41256 m3/kmol
kDBT,τ ) 3.08384 × 10-1 kmol/(kgcat h)
kBPH,τ ) 1.69206 kmol/(kgcat h)
kCHB,τKCHB,τ ) 3.38631 × 10-1 m3/(kgcat h)

(-∆H0a), and for the adsorption entropies (-∆S0a) men-

tioned in Froment and Bischoff (1990) were satisfied:

Ea > 0

(-∆H0a) > 0

0 < (-∆S0a) < S0g

48.14 < (-∆S0a) < 51.04 + 0.0014(-∆H0a)

The values for the adsorption equilibrium constants and

for the rate coefficients at 573 K are given in Table 2.
The adsorption of DBT, BPH, and hydrogen is stronger
on the σ sites than on the τ sites. The significant
differences between KDBT,σ and KDBT,τ, between KBPH,σ
and KBPH,τ, and between KH,σ and KH,τ are a posteriori
evidence for the distinction between sites for hydro-
genolysis and hydrogenation.
The adsorption entropy (-∆S0a) for BPH, H2, and
H2S on the σ sites was calculated to be 65.4, 100.3, and
150.0 kJ kmol-1 K-1, respectively; the adsorption en-
tropy (-∆S0a) for DBT, BPH, and H2 on the τ sites was
126.4, 63.3, and 142.2 kJ kmol-1 K-1, respectively.
Activation energies for DBT hydrodesulfurization pre-
sented in the literature are between 60 and 163 kJ/mol
(Broderick and Gates 1981; Edvinsson and Irandoust,
1993; O’Brien et al., 1986; Singhal et al., 1981; Vrinat, Figure 7. Parity plots for RDBT (a) and RBPH (b).
1983). The heat of adsorption for DBT and H2 reported
in the literature range from 18.8 to 51.8 kJ/mol and from Toyoshima and Somorjai (1979) found a value of 146.5
25.1 to 138.5 kJ/mol (Broderick and Gates, 1981; Ed- kJ/mol as the heat of adsorption for H2. The values
vinsson and Irandoust, 1993; O’Brien et al., 1986; presented in this paper are in good agreement with the
Singhal et al., 1981; Vrinat and de Mourgues, 1981). values reported in the literature.
 Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996 3317
Acknowledgment

This work was funded by the European Commission

under the Joule Program Contract JOU2-0121. V.V. is
also grateful for a contribution from the Center of
Excellence Grant awarded to the Laboratorium voor
Petrochemische Techniek by the Belgian Ministry of
Science.

Nomenclature
Ci ) liquid concentration of component i, kmol/mL3
Ea ) activation energy, kJ/kmol
Fgi ) molar gas flow rate of component i, kmol/h
Fli ) molar liquid flow rate of component i, kmol/h
0
FDBT ) molar feed flow rate of dibenzothiophene, kmol/h
(-∆H0a) ) heat of adsorption, kJ/kmol
ki,s) rate coefficient of component i on s sites, kmol/(kgcat
h)
Ki,s ) adsorption coefficient of component i on s sites, mL3/
kmol
n ) number of experiments
ns ) number of replicated experiments
p ) number of parameters
pt ) total pressure, bar
rBPH,τ ) rate of hydrogenation of biphenyl into cyclohexyl-
benzene, kmol/(kgcat h)
rCHB,τ ) rate of hydrogenation of cyclohexylbenzene into
bicyclohexyl, kmol/(kgcat h)
rDBT,σ ) rate of hydrogenolysis of dibenzothiophene into
biphenyl, kmol/(kgcat h)
rDBT,τ ) rate of hydrogenation of dibenzothiophene into
tetra- and/or hexahydrodibenzothiophene, kmol/(kgcat h)
RDBT ) total rate of disappearance of dibenzothiophene,
kmol/(kgcat h)
Rgas ) gas constant, kJ kmol-1 K-1
Ri ) net production rate of component i, kmol/(kgcat h)
S(θ) ) objective function
(-∆S0a) ) adsorption entropy, kJ kmol-1 K-1
T ) absolute temperature, K
Tm ) average temperature, K
Figure 8. Parity plots for RCHB (a) and RBCH (b). v ) number of responses
xBCH ) conversion of dibenzothiophene into bicyclohexyl
The comparison between the experimental values Ri xBPH ) conversion of dibenzothiophene into biphenyl
and the calculated values R̂i are shown in Figures 7 and xCHB ) conversion of dibenzothiophene into cyclohexylben-
8. As can be seen from these figures, there is a very zene
xDBT ) conversion of dibenzothiophene
good agreement between the experimental values and
W ) total catalyst mass, kgcat
the model predictions.
Greek Symbols
Conclusions γ ) molar hydrogen to hydrocarbon ratio in the feed
σ ) hydrogenolysis site
The kinetic study of the hydrodesulfurization of σhk ) (h,k) element of the inverse of the covariance matrix
dibenzothiophene pointed out that hydrogenolysis and of the experimental errors on R
hydrogenation reactions occur on two different types of τ ) hydrogenation site
active sites. On both types of active sites the surface Subscripts
reactions between adsorbed reactants and two competi- BCH ) bicyclohexyl
tively adsorbed hydrogen atoms were rate determining. BPH ) biphenyl
Dibenzothiophene undergoes hydrogenolysis with or CHB ) cyclohexylbenzene
without prior hydrogenation of the aromatic ring sys- DBT ) dibenzothiophene
tem. Similar rate equations were derived by Van Parys H ) atomic hydrogen
and Froment (1986) for the gas phase HDS of thiophene H2 ) molecular hydrogen
and by Van Parys et al. (1986) for the gas phase HDS H2S ) hydrogen sulfide
of benzothiophene. Under identical operating condi- σ ) with respect to the hydrogenolysis function
tions, the intrinsic rate of thiophene hydrogenolysis was τ ) with respect to the hydrogenation function
found to be higher than that of benzothiophene hydro- Superscripts
genolysis. The rate of dibenzothiophene hydrogenolysis
ˆ ) calculated
as determined from the multiphase experimentation of g ) gas
this work was lower than that of thiophene and ben- l ) liquid
zothiophene.
3318 Ind. Eng. Chem. Res., Vol. 35, No. 10, 1996
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Received for review February 9, 1996
Revised manuscript received May 14, 1996
Accepted June 12, 1996X
IE960099B
X Abstract published in Advance ACS Abstracts, September
1, 1996.