You are on page 1of 15

® 1997 Elsevier Science B. V. All rights reserved.

Hydrotreatment and hydrocracking of oil fractions


G.F. Froment, B. Delmon and P. Grange, editors 83

Kinetics of the catalytic removal of the sulphur components from the light cycle
oil of a catalytic cracking unit

G.F. Froment, G.A. Depauw and V. Vanrysselberghe

Laboratorium voor Petrochemische Techniek, Rijksuniversiteit Gent, Krijgslaan 281,


B-9000 Gent, Belgium

ABSTRACT

First order kinetics for the hydrodesulphurization of 40 sulphur components of the


benzothiophene and dibenzothiophene families were determined using experimental data
obtained with a light cycle oil. Substituents next to the sulphur atom reduce the reactivity with
respect to the nonsubstituted component. Hougen Watson rate equations for substituted
dibenzothiophenes were related to those for the head of the family, dibenzothiophene, through
global multiplication factors f„ s^ny ^"^ frsDUT- These factors are the products of the electronic
and steric effects of the substituents on the adsorption equilibrium constants and of the
electronic effects on the rate coefficients. They were evaluated for a number of substituted
dibenzothiophenes.

1. INTRODUCTION

Light cycle oil (LCO) contains various aromatic sulphur components such as
benzothiophenes (BTs), dibenzothiophenes (DBTs) and naphthothiophenes [1]. These
components have to be removed for both technical and environmental reasons. Hence the
sulphur content of diesel is limited to 0.05wt% from October 1996 onwards.
Detailed kinetic equations for the sulphur components are required for the modeling of
the trickle bed reactors used for hydrodesulphurization (HDS). LCO is an ideal feedstock for
the determination of the kinetic data since all interesting refractory sulphur components are
present in it and since the content of aliphatic sulphur components as well as the length of the
alkyl side chains are limited, thus facilitating the quantification.
A kinetic modeling of the hydrodesulphurization reactions based upon structural
contributions was developed to limit the number of parameters [2]. The rates for reactions
involving substituted components were related to those of a non substituted reference
component in terms of the effect of the substituents on the rate coefficients and the adsorption
equilibrium constants. Based upon a number of assumptions, multiplying factors were
introduced for the electronic and steric effect of the substituents on the adsorption and for the
electronic effect on the reaction rate. In that way the number of parameters for the HDS of
a set of mono-, di- and trimethyl substituted DBTs was reduced from 1133 to 93. According
to the rate equations derived for the HDS of DBT [3] and assuming that the rate expressions
84

for the HDS of the methyl substituted DBTs are of an identical form, this number can be
further reduced to 35.
A limited set of experiments with complex mixtures, such as LCO, can be used to
obtain the global multiplication factors for various components. These global factors are the
products of the effects of the substituents on both the rate coefficients and the adsorption
equilibrium constants. The determination of the structural contributions as defined by
Froment et al. [2] requires additional experimental data obtained from model components
such as 4-methyldibenzothiophene (4-MeDBT), 4,6-dimethyldibenzothiophene
(4,6-DiMeDBT) and one of the trimethyldibenzothiophenes.

2. EXPERIMENTAL SET-UP

The liquid hydrocarbon was fed into the reactor with a high-pressure pump. The
hydrogen, the hydrogen sulphide and the nitrogen feed were controlled and metered with a
set of electronic mass flow controllers. Hydrogen sulphide and nitrogen were used in the
pretreatment of the catalyst. The gases and the liquid feed were preheated and mixed before
entering the reactor. The effluent section was also heated to avoid condensation. The reaction
was carried out in a multiphase Robinson-Mahoney reactor. The temperature was measured
by means of thermocouples and controlled by a PID temperature controller. The pressure was
controlled by a back pressure regulator. 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. The liquid was collected in the liquid holder. The cyclone and the liquid holder were
kept at the same pressure and temperature as in the reactor, to avoid changes in composition
of both phases. The gas phase was cooled, so as to condense heavy fractions, and was then
scrubbed by means of a sodium hydroxide solution to remove hydrogen sulphide before
venting. The liquid product was cooled and flashed under ambient conditions. The light gases,
dissolved in the liquid phase, were partially desorbed and collected in a gas burette. Product
samples were taken off-line for GC analysis.

3. ANALYSIS

The GC-AED system (Hewlett-Packard 5921 A) was used for the quantification of
sulphur components and the determination of the total sulphur content of the LCO mixture.
The atomic emission detector (AED) is element specific and has a high dynamic range for
C, H, N and S. The total sulphur content of the LCO (1.28wt%) was determined with the
AED using hydrogen linearization. Detailed identification and quantification results of the
sulphur components in LCO are presented in a separate paper by Depauw and Froment [1].
A quadrupole mass spectrometer, part of the Hewlett-Packard 5989A system was used
for quantification as well. Electron impact ionisation mass spectra (m/z 40-400) were obtained
at 70eV at a rate of 1.6 scans/second. The quadrupole temperature was lOO^'C, the ion source
temperature 250''C and the transfer line temperature 250''C. The GC separation was
performed with a Hewlett-Packard 5890 Series 11 instrument on a 50 m x 0.2 mm fused silica
capillary column coated with a 0.5 ^m film of cross linked 100% dimethylsiloxane (HP-
PONA). Helium was used as carrier gas (0.645 ml/min at 35''C). The column was
85

temperature programmed from 35°C(5 min) to SCCCIS min) at a rate of 2.5°C/min and
further to 200°C(5 min) at a rate of 2.0°C/min and finally to 250X at a rate of TC/min.
The injector temperature was 250°C. One microliter of undiluted sample was injected at a
split ratio of 63:1.
The conversion of a molecule can be calculated by comparing the feed and effluent ion
chromatograms. The effluent chromatograms are scaled using fluorene as an internal
standard. This molecule is present in the LCO feed and is not produced nor hydrogenated or
evaporated significantly under reaction conditions. It does not co-elute with other components
with the same mass. The most important fragment of fiuorene with a m/z ratio of 166 was
used for the scaling. An ion chromatogram (m/z =166) of an effluent is multiplied with a
scaling factor in order to get the same surface for the fluorene peak as was obtained for this
peak in the feed analysis. All other ion chromatograms of the effluent are multiplied with the
same factor. The surfaces of the peaks in the effluent and the feed ion chromatograms are
then linearly proportional in an identical way to the molar flows at the reactor exit and
entrance respectively. The conversions of all components in the feed are derived from the
relative decrease of their fragments. In case of co-elution of several molecules an ion
fragment which is typical for the molecule considered has to be used for the calculations of
the conversion.

4. EXPERIMENTAL PROGRAM

Experiments were performed with a light cycle oil (LCO) of a catalytic cracking unit
containing 1.28wt% sulphur and with a boiling range of 225-370''C. Experiments were
carried out at temperatures between 240 and 320°C. The liquid pumping rate was varied
between 15 and 27 ml/hr. The total pressure was 80 bar, and the hydrogen to hydrocarbon
ratio 344 Nl/1. The molar hydrogen to methane ratio was 6.4. The number of experiments
amounted to 25.
The catalyst used was the commercial HDS catalyst AKZO Ketjenfine 742. It was
crushed to a size between 710 and 800jitm to avoid diffusional limitations and 2.53 gcat were
diluted with nonporous inert alumina. The absence of diffusional limitations was calculated
using the Weisz-Prater criterion.
The reaction mechanism and the intrinsic kinetic equations for the hydrodesulphurization
of dibenzothiophene were derived by Vanrysselberghe and Froment [3].
In order to determine the kinetics for the hydrogenation of naphthalene into tetralin,
experiments were carried out using a solution of 2wt% dibenzothiophene and l-5wt%
naphthalene in a paraffinic mixture (Cjo-CiJ. The temperature was varied between 240 and
300''C, the molar hydrogen to hydrocarbon ratio between 1.10 and 1.36. The molar feed flow
rate of dibenzothiophene was varied between 1.23 10'^ and 3.94 10'^ kmol/hr, the naphthalene
molar feed flow rate between 1.71 10'^ and 1.42 lO'** kmol/hr. The total pressure was 80 bar.
86

5. RESULTS AND DISCUSSION

5.1. First order kinetics


In order to compare the kinetic data obtained in this work with literature data and to
provide quantitative results on the reactivity, first order rate coefficients were determined
from the experimental conversions. The conversion X; of component i is defined as:

pj. in T; out

X.= ^ ' (1)

The conversion Xj of component i is directly obtained from the experimental data. The
continuity equation for this component in the perfectly mixed reactor is given by:

F/"-r.W=Fr (2)

Substitution of (2) into (1) results in:

r.W
with Fi'"=V'"Ci'" (3)

Using the first order approach, the rate of removal is assumed to have the form:

r=k.C.
I I
(4)

The ratio of the concentration of i at reactor conditions and in the inlet CJC-^ can be written
as (l-Xi)pV"'/p"'V°"^ The rate coefficient is finally written as a function of measured
quantities:

k.=—L-l-^ (5)
' 1-Xj W p

The activation energy and preexponential factor are determined from the Arrhenius
relationship:

krAiexp(-JfL) (6)
87

Results for the BT-family

The results for 27 sulphur components of the BT-family are presented in Table 1. The
conversions used for the determination of these properties were obtained with the GC/MS
system, which shows less peak overlapping than the GC-AED analysis. The Arrhenius plots
for a set of substituted benzothiophenes are shown in Figure 1. The correlation coefficients
R^, the ratio of the regression sum of squares to the total sum of squares, varied from 0.986
for 7-EtBT to 0.999 for 2567-TeMeBT.

Table 1
Preexponential factors, activation energies and first order rate coefficients at T=280°C for
various members of the BT-family

Sulphur component A, [mVkg,,yh] E,i [kJ/kmol] k, [mVkg,,,/h]

atT=280°C

BT 6.537 10^^' 121100 2.587 10'


54-6-MeBT 4.253 10' 107900 3.109 10'
3+4-MeBT 8.687 10' 85900 8.737 10-2
7-MeBT 2.025 10' 113300 5.059 10-2
27-DiMeBT 2.717 10^' 187000 6.591 10-^
23-DiMeBT 5.511 lO''* 179100 9.990 10-'
2-EtBT 2.173 10' 88200 1.016 10'
7-EtBT 2.394 10^« 125300 4.645 10-2
24-DiMeBT 4.412 10'" 172400 2.852 10-2
56-DiMeBT 7.423 10' 112200 1.885 10'
45-DiMeBT 9.943 10' 115900 1.087 10'
34-DiMeBT 6.025 10*^ 87170 3.345 10-2
35-h36-DiMeBT 3.717 10^2 142100 1.921 10'
257-TriMeBT 5.102 10'" 178400 8.197 10-'
357-TriMeBT 1.212 10^" 123500 3.180 10-2
267-TriMeBT 4.371 10'^ 147500 6.515 10-'
356-TriMeBT 1.528 10" 130100 8.258 10-2
234-TriMeBT 9.660 10'' 210000 1.363 10-2
235+236-TriMeBT 1.816 10'2 150200 1.382 10-2
7-PrBT 8.112 10'^ 171100 5.840 10-2
2357-TeMeBT 2.026 10'^ 142600 7.185 10-'
2367-TeMeBT 5.629 10*2 159700 4.906 10-'
2567-TeMeBT 5.297 10'" 134400 1.147 10-2
88

1/T(*1000)(K'^)
1.78 1.83 1. 1.93
H h

• 27-DMBT 1
B 7-MBT
A 2367-TMBT
xBT
X 356-TMBT
• 2567-TMBT
+ 7-EBT
- 235+236-TMBT
- 56-DMBT
o 45-DMBT
D 357.TMBT
1 A 257-TMBT

Figure 1 Arrhenius plots for a set of components of the BT-family.

Components with substituents in position 2 show an important decline in reactivity with


respect to benzothiophene. This is less pronounced for substituents in position 7 and position
3. The decline in reactivity due to substitution in position 2 and 7 is caused by the steric
hindrance of these substituents on the vertical adsorption through the sulphur atom. A
substituent in position 3 causes steric hindrance on the adsorption through the double bond
of the thiophenic ring. Substituents in the positions 4, 5 and 6 hardly affect the reactivity of
the component. The first order rate coefficients of the methyl substituted benzothiophenes can
be related to the rate coefficient of benzothiophene as follows:

1. AAAJAAA^ (7)
Kj-r2l7 131415 16 Kjj

where f4=f5=f6. The power 6j equals one if the substituted BT contains a methyl substituent
in position j , otherwise 5j is zero. The product f2'f7Y3'f4'fJ*f6' 's a global multiplication factor
if the removal of the benzothiophenes occurs mainly on one type of catalytic site. The
parameters fj were obtained by minimization of the objective function:
89

A
2:[ln(iL)-ln(^)]^ ^^^
>=1 '^BT BT

where n=23. The parameter estimates for T=240X, T=260°C, T=280°C and T=300X
are given in Table 2. The parameters f, could not be determined at T=320°C because
benzothiophene was completely converted at this temperature for the flow rates that could be
applied in the equipment.

Table 2
Values of the fj parameters of the rate coefficient prediction model for four temperatures.

Parameter T=240X T=260°C T=280°C T=300°C

f2 0.0479 0.0882 0.125 0.183


h 0.334 0.295 0.298 0.318
f3 0.395 0.429 0.481 0.609
f4 = f5 = f6 1.078 0.871 0.886 0.807

The calculated versus experimental first order rate coefficients for the substituted BTs
are shown in Figure 2 for all temperatures. The correlation coefficient R^ is 0.973. From the
parameter values of Table 2 it is seen that a methyl substituent in position 2 reduces the
reactivity at T=240''C with 95% with respect to BT. For methyl groups in positions 7 and
3 the reduction at T=240°C is respectively 67% and 61 %. The effect predicted by the model
of the 4, 5 and 6 methyl substituents is a small increase at T=240°C and a reduction in
reactivity at the other temperatures. The l, parameter values increase with temperature for
substituents on the thiophene moiety and tend to decrease for substituents on the benzene
moiety.

Results for the DBT-family

These results are given in Table 3. Houalla et al. [4] determined first order rate
coefficients for DBT, 4-MeDBT and 4,6-DiMeDBT at 300''C and 102 bar on a C0M0/AI2O3
catalyst. The ratio between the rate coefficient of the substituted DBT and DBT obtained by
Houalla et al. [4] and in the present work is given in Table 4. The ratios for 4-MeDBT and
4,6-DiMeDBT are higher than those found by Houalla et al. [4] The reactivity obtained for
4-MeDBT with respect to 4,6-DiMeDBT is almost 3 in this work and 1.35 according to the
results of Houalla et al. [4]
90

Calculated ki [m^ /kg cat hr]


1

0.001 0.003 0.01 0.03 0.1 0.3


Experimental ki [m^ /kgcathr]

Figure 2 Calculated versus experimental first order rate coefficients at all temperatures for
components of the BT-family.

Table 3
Preexponential factors, activation energies and first order rate coefficients at T=320°C for
various members of the DBT-family.

Sulphur component A; [mVkg^Jh] E,i [kJ/kmol] ki [m'/kg^/h]

atT=320°C

DBT 3.974 10' 64700 1.064 10-'


1-MeDBT 1.717 10' 57800 1.892 10'
2+3-MeDBT 7.579 la' 91400 1.035 10'
4-MeDBT 1.181 10" 76850 2.115 10-'
46-DiMeDBT 5.161 10' 54100 8.152 10-"
24-DiMeDBT 3.371 10^ 59400 3.457 10-'
13-DiMeDBT 5.421 10' 96300 2.253 10-'
23-DiMeDBT 4.714 10" 72500 2.566 10'
4-PrDBT 5.220 10' 48700 3.060 10'
4Et6MeDBT 5.499 10' 63900 1.174 10-'
146-TriMeDBT 2.364 10' 59300 1.821 10-'
346-TriMeDBT 9.252 10" 82700 4.733 10'
91

Table 4
Comparison of the reactivities found by Houalla et al. [4] and the present work at T = 3 0 0 X
for 4-MeDBT and 4,6-DiMeDBT with respect to DBT

llaetal. [4] Present work


'^-MeDBT'l^DBT 0.090 0.35
0.067 0.12

5.2. Hougen Watson kinetics

Introduction

Aromatic sulphur components are converted on a sites by hydrogenolysis and on r sites


by hydrogenation. Several authors [3,5,6] found for the HDS of benzothiophene and
dibenzothiophene that the surface reaction between adsorbed species is the rate determining
step on both sites. The resulting Hougen Watson rate equation is generalised here for all
aromatic sulphur components. The rate equation for the disappearance of an aromatic sulphur
component i in a complex mixture becomes:

K^\o^Ha^i ^H, ^r^ir^Hr^i ^H,


r.=- (9)
' DEN„(T,C„...,C„) DEN^(T,C„...,C„)

where the first term relates to the hydrogenolysis and the second to hydrogenation. The
adsorption characteristics on both catalytic sites differ, as reflected by the denominators DEN„
and DEN^. These contain the concentrations of all adsorbing species and their temperature
dependence. The functions represented by DEN„ and DEN^ are identical for all rate
equations.
Hydrogenation reactions of aromatics occur only on the r sites. The surface reaction
was observed to be the rate determining step for biphenyl [3,6] and naphthalene
hydrogenation. Since the hydrogenation reactions are irreversible their rate can be written:

_ k..K.^K„^C. C^ ^^^^
' DEN^(T,Cp...,C„)

The rate equations for the hydrogenation of sulphur components and aromatics contain the
same denominator DEN^.

Determination of the denominators DEN,, and DEN,

In complex mixtures the denominators DEN,, and DEN^ cannot be calculated a priori,
since not all adsorbing species and their corresponding adsorption equilibrium constants are
92

known. Relating the rates of substituted sulphur components in complex mixtures to those of
the unsubstituted heads of the families, requires the knowledge of both denominators DEN„
and DEN^ for each LCO experiment. For the complex mixture LCO these can be calculated
considering model components for which kj^Kj^KH^ and kj^Kj^Hr ^^^ known, since these
products are invariant of the mixture composition. The product k,)BT„K[)BT^KH„ was determined
for the hydrogenolysis of dibenzothiophene [3]. The products k^mTT^Dm^Hr^ kupH^BPHr^HT
and kN^Nr^Hr were determined for the hydrogenation of dibenzothiophene [3], biphenyl [3]
and naphthalene in the present work. These products can be substituted in the rate equations
of the reactions of dibenzothiophene and naphthalene in the LCO mixture. Now the
denominators of the rate equations of these model components can be calculated. These
denominators DEN„ and DEN^ are identical for the rate equations of all the sulphur
compounds in the LCO. The expressions for the conversion of DBT, the conversion of DBT
into biphenyl and cyclohexylbenzene, the conversion of naphthalene and the conversion of
naphthalene into tetralin in a LCO in the completely mixed reactor can be written:

(11)
" " ^ " " C ^ V ^ DEN„(T,C„...,C„) DEN/T,C„...,C„)

_ W ^ H , J- ^ D B T o ^ D B T o ^ H o ^ D B T _ * ^ B P H T ^ B 1 » H T ' ^ H r ^ B P H -I
(12)

'"'" C ^ V^ DEN„(T,C„...,C„) " DEN,(T,C„...,C„)^


(13)

" " ' c £ v ^ DEN,(T,C, C.) DEN,(T,C Cj'


. . - ^ % NT NT HT
(14)
" c^ V^'DEN^(T,C„...,C„)^

(15)
C ; V-^DEN/T,C„...,C„)^

with

V„„ =2.44 10'» exp[. -122.8 10^ ] kmol/kgjh

KH„ =3.36 10-" exp[ilM_!2!] m'/kmol


KJ
K„„T„ =7.57 10' mVkmol

ko„, =2.87 10'* exp[Zl^^4^] k'1101/kg.a/h


KJ
k„p„^ =3.41 10" exp[-^^Jiy^] kmol/kgjh
KJ
93

K„, =1.40 10-" e x p [ i i | i L l ^ ] mVkmol

76.8 10^
K^^^ =2.50 10-' exp[ ] m'/kmol

K „ _ =4.97 10-" exp[ 37.9 10^ ] m'/kmol

-185.9 10^
k^, =1.57 10" exp[- ] kmol/kgjh

K^, =5.06 10-' e x p [ ^ 4 ^ i ^ ] mVkmol


R,a.T

The values of the unknowns, DEN„ and DEN^ were estimated for each LCO experiment
by means of regression. They are shown in Figures 3 and 4 at T=320°C for various liquid
compositions expressed in terms of a molar averaged conversion defined as follows:

1
X =
E ^i y* (16)
Eyi

with Xj the conversions of a set of selected components (BT, DBT, Naphtho[2,/-Z7]thiophene,


4-MeDBT, 4,6-DiMeDBT, Naphthalene and Phenanthrene) and yj the corresponding mole
fractions in the LCO feed.
The adsorption is weaker at higher temperatures on both the r and a sites and the
denominators decrease. For a given temperature, the coverage of the r sites increases and that
of the a sites decreases with molar averaged conversion. The reacting species in the LCO
mixture adsorb to a higher extent on the a sites than the reaction products.

220

200

27 30 33 27 30 33
Molar averaged conversion [%] Molar averaged conversion [%]
Figure 3: Denominator corresponding Figure 4: Denominator corresponding
to the c7-sites at T=320°C as a function to the T-sites at T=320°C as a Function
of the molar averaged conversion. of the molar averaged conversion.
94

Determination of multiplication factors

In a second step the numerical values of both denominators can be used in the rate
equations of substituted aromatic sulphur components. The rate equations for these substituted
sulphur components, sDBT e.g., can be related to that of the unsubstituted head of the family,
DBT [2]:

f ]c K K f \c K K

fsDBT-^sDBT ^",1 pEN (T,C„...,C„) DEN,(T,C„...,C„) ^

The global multiplication factors f„ ^DBT and f^soBT are the products of the electronic and
steric influences of the substituents on the adsorption equilibrium constant and of the
electronic effects on the rate coefficient. These factors depend on the temperature. The
conversion of a sDBT in a completely mixed reactor can then be written:

_ ^ ^sDBT Hj |. *asDBT^DBTo ^ D B T o Ho TSDBT^DBTT ^ D B T T ' ^ H T - . /1 0\

^ ° ' ' ^ ~ C ^ V^ DEN„(T,C„...,C„) DEN/T,C„...,C„)^

The global multiplication factors f^ SDBT and frsDBT are the unknowns in this equation. As
mentioned ^mja^mTcf^Ha and kj)j,T^t)j,TrKHr were already derived by Vanrysselberghe and
Froment [3]. The denominators were determined for the compositions reached in each LCO
experiment as explained above. The multiplication factors at a given temperature are obtained
by minimization of the objective function:

/ ^ (^SDBT"^.S[)BT) ^ ^

where X',DBT are the experimental conversions. In Table 6 the global multiplication factors
t,i)BT and t,[)BT at T=320X are given for 4-MeDBT, for 4,6-DiMeDBT and for 2 and 3-
MeDBT which were not separated by GC-MS.

6. CONCLUSIONS

The reactivity of various sulphur components of the benzothiophene and


dibenzothiophene family has been demonstrated using first order rate coefficients. Substituents
next to the sulphur atom reduce the reactivity with respect to the unsubstituted component.
Substituents in other positions can either increase or decrease the reactivity. The electronic
and steric influences of the substituents on the rate coefficient and the adsorption equilibrium
95

Table 6
Global multiplication factors f„,i,BT and t,^,^ at T=320°C for 2+3-MeDBT, 4-MeDBT and
4,6-DiMeDBT.

Component K sDHT I i sDBT

2+3-MeDBT 1.3 1.1


4-MeDBT 0.15 3.3
4,6-DiMeDBT 0.037 1.8

constant in the more refined approach of Froment et al. [2] were combined into global
multiplication factors f„ .DBT and f^ ^DBT i^ the Hougen Watson rate equations. The
denominators corresponding to the a and r sites in the LCO can be obtained by using the
Hougen Watson rate equations of the hydrodesulphurization of dibenzothiophene and the
hydrogenation of naphthalene into tetralin. The a sites were found to be more occupied than
the T sites. The global multiplication factors can be determined in a next step using the
numerical values for the denominators.
The next level of refinement involves the determination of the structural contributions
as defined by Froment et al. [2]. This approach requires experimental data with 4-MeDBT,
4,6-DiMeDBT and one of the trimethyldibenzothiophenes as model components. The
contributions kELo''''''(m;0;0), k^J'''''(n\;0;0), Ki,L+sTr''''''(m;0;0) and the product
KsTa^^'^(4;0;0)KELo^"'^(m;0;0) can be obtained from experiments with 4-MeDBT. Combining
these results with the global multiplication factors obtained with the LCO experiments,
KsTa^*^^(4;0;0) can be calculated by dividing the global multiplication factor fs^DBx for
4-MeDBT by that for the 1, 2 or 3-MeDBT. An identical approach has to be followed to
determine the structural contributions for the di- and trimethylDBTs.

ACKNOWLEDGEMENT

This work was funded by the European Commission under the Joule program contract
no. JOU2-0121. V. Vanrysselberghe and G.A. Depauw are also grateful for a contribution
from the Center of Excellence Grant awarded to the Laboratorium voor Petrochemische
Techniek by the Belgian Ministry of Science. We wish to thank R. Le Gall for his
cooperation.

REFERENCES

L G.A. Depauw and G.F. Froment, Journal of Chromatography, to be published.

2. G.F. Froment, G.A. Depauw and V. Vanrysselberghe, Ind. Eng. Chem. Res., 33 (1994)
2975.
96

3. V. Vanrysselberghe and G.F. Froment, Ind. Eng. Chem. Res., to be published.

4. M. Houalla, D.H. Broderick, A.V. Sapre, N.K. Nag, V.H.J. De Beer, B.C. Gates, and
H. Kwart, J. of Catal., 61 (1980) 523.

5. I.A. Van Parys and G.F. Froment, Ind. Eng. Chem. Prod. Res. Dev., 25 (1986) 431.

6. R. Edvinsson and S. Irandoust, Ind. Eng. Chem. Res., 32 (1993) 391.

NOMENCLATURE

Ai preexponential factor m-Vkg,,yh


liquid concentration of component i
c> inlet liquid concentration of component i kmol/mL^
Eai activation energy kj/kmol
pin
inlet molar liquid flow rate of component i kmol/h
pout kmol/h
outlet molar liquid flow rate of component i
kE.."»T(m;0;0)
electronic effect of one methyl group on the rate
coefficient for the hydrogenolysis of sDBT
W,™^(m;0;0) electronic effect of one methyl group on the rate
coefficient for the hydrogenation of sDBT
first order rate coefficient of component i mVkgJh
rate coefficient of component i on s sites kmol/(kg,,ih)
K,J«'T(m;0;0) electronic effect of one methyl group on the adsorption
equilibrium constant of sDBT on the a sites
KE,,.sT.™^(ni;0;0) electronic and steric effect of one methyl group on the
adsorption equilibrium constant of sDBT on the r sites
K.sT„""(4;0;0) steric effect of a methyl group in position 4 on the
adsorption equilibrium constant of sDBT on the a sites
adsorption equilibrium constant of component i on s mL^/kmol
sites
•^gas gas constant kJ/kmol/K
total rate of disappearance of component i kmol/(kg,,ih)
T absolute temperature K
yin total inlet volumetric liquid flow rate mVh
yout total outlet volumetric liquid flow rate mVh
w total catalyst mass kgcat
XfiPH conversion of dibenzothiophene into biphenyl
^CHB conversion of dibenzothiophene into cyclohexylbenzene
^DBT conversion of dibenzothiophene
^sDBT conversion of substituted dibenzothiophene
conversion of component i
conversion of naphthalene
conversion of naphthalene into tetralin
calculated conversion of substituted dibenzothiophene
97

GREEK SYMBOLS

p liquid density at reactor conditions kg/m^


p^ inlet liquid density kg/m^
a hydrogenolysis site
r hydrogenation site

SUBSCRIPTS

BPH biphenyl
CHB cyclohexylbenzene
DBT dibenzothiophene
H atomic hydrogen
H2 molecular hydrogen
a with respect to the hydrogenolysis function
r with respect to the hydrogenation function

SUPERSCRIPTS

^ calculated
in inlet conditions
out outlet conditions