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Ind. Eng. Chem. Res.

1994,33, 2975-2988 2975

Kinetic Modeling and Reactor Simulation in Hydrodesulfurization


of Oil Fractions?
Gilbert F. Froment; Guy k Depauw, and Valerie Vanrysselberghe
Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B-9000 Gent, Belgium

An adiabatic multiphase reactor for diesel hydrodesulfurization (HDS) was simulated with a
one-dimensional heterogeneous model. A diesel-type mixture containing benzothiophene,
dibenzothiophene, and 4,6-dimethyldibenzothiophenea s sulfur components and quinoline as
nitrogen component was chosen as feed. A kinetic modeling for the HDS of dibenzothiophene
and alkyl-substituted dibenzothiophenes based upon structural contributions was developed.
According to a molecular approach the total number of rate and adsorption parameters for the
HDS of a set of (substituted)-dibenzothiophenesis 1133. In the structural contribution approach
introduced here the total number of parameters has been reduced to 93.

Introduction complex mixture of sulfur- and nitrogen-containing


components.
Sulfur is present in many forms in petroleum frac-
tions: mercaptans R-SH, sulfides R-S-R', disulfides Scrutiny of Reactor Modeling Aspects
R-S-S-R, polysulfides R-S,-R', thiophene, ben-
zothiophene (BT), dibenzothiophene (DBT), and their Reactor Model Equations. The hydrodesulfuriza-
alkyl derivatives. In addition, various nitrogen-contain- tion of diesel fractions is performed in a multiphase
ing components like pyridine and alkylpyridines, quino- fxed bed reactor. Three phases are present in the
line and alkylquinolines, benzoquinolines, acridines, reactor: the fmed bed of porous catalyst particles, a
indoles, and carbazoles are also present. vapor phase, and a liquid phase flowing cocurrently
Sulfur has to be removed from oil fractions for both downward. The liquid feed is usually a blend of
technical and environmental reasons. The specifica- straight-run gas oil and light cycle oil from a FCC or
tions on diesel for example are getting more stringent. coker unit. The sulfur content of the liquid feed is
From October 1993 onward the sulfur content of diesel typically 0.5-2.0 wt %. It is reduced by the hydrotreat-
for highway traffic is limited to 0.05 w t % in the United ment to 0.2-0.05 wt %. The gas phase consists mainly
States. At present the maximum sulfur content in of hydrogen, hydrogen sulfide, ammonia, and vaporized
Western Europe is 0.2-0.3 wt %, depending upon the diesel components. The liquid phase consists of the gas-
country, but the specification imposed by the European oil components, including the sulfur- and nitrogen-
Union from Oct 1, 1996, onward for class 3 standard containing components and dissolved gases like hydro-
diesel for long-haul traffic and off-highway applications gen, hydrogen sulfide, ammonia, and light hydrocarbons.
is 0.05 wt % S. For class 1and 2 diesels, which will be In commercial applications trickle and pulse flow are
used for transportation buses and cars in urban areas, the most likely flow regimes. Trickle flow features are
the limits will be respectively 0.001 and 0.03 wt % S. a continuous gas phase and a dispersed liquid phase
This is a serious challenge. Are the present-day cata- flowing as a laminar film or as rivulets over the
lysts adequate for reducing the sulfur content to such particles. The pulse flow regime is obtained a t higher
levels? Can modeling and simulation contribute to the liquid and gas throughputs. According to Wammes et
new developments? What is the level of sophistication al. (1990) the pulse flow regime is not attained at high
that has to be introduced in the reactor model? The pressures and realistic liquid flow rates, if the molecular
weight of the gas phase is of the order of that of
hydrodynamics in HDS reactors is not well understood. nitrogen. In a hydroprocessing unit operating, for
Calculating accurate thermodynamic properties for such example, at 310 "C and 50 bar, the molecular weight of
complex mixtures is another problem. Kinetics is a the gas phase is approximately 20 g/mol. Therefore,
major element of reactor modeling and simulation. The strong indications exist that trickle flow is the dominat-
literature on the conversion of key componentsis rather ing flow regime. Besides, it is commonly accepted that
abundant, but the information is seldom coordinated. in commercial hydroprocessing reactors all the particles
Most of the rate equations published to date are simple are completely wetted when the gas and liquid are
first order disappearance kinetics. The rate of HDS of adequately distributed (Shah, 1979). The model devel-
the oil fraction is then generally lumped into a single oped in the following pages is a one-dimensional het-
second order reaction, to account for the large variation erogeneous model with both the gas and liquid phase
of the reaction rates of the various feed components. The in plug flow (Froment and Bisschof, 1990). The steady
developmentof deep HDS processes imposed by the new state continuity equation for a component i of the gas
specifications will definitely require more accurate phase can be written as
kinetics. The present paper deals with various aspects
of the simulation of an adiabatic multiphase reactor for
diesel desulfurization and with the derivation of a set 1 dF,G
2 = 1,..., N (1)
of adequate kinetic equations for the conversion of a szdz

atz=O F.
rG
=F".
LG
t Presentedat the Symposium on Catalytic Reaction Engi-
neering for Environmentally Benign Processes at the San
Diego ACS Meeting, March 13-18, 1994. The liquid phase and the gas phase are not necessarily
0888-5885I94l2633-2975$04.50/0 0 1994 American Chemical Society
2976 Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994

in equilibrium. The molar flow rate of a component i The effective diffusivity accounts for the porosity of the
in the gas phase ( F ~ Gcan
) only change by transfer to or catalyst particle and for the tortuosity of the pore
from the liquid phase, since the gas phase only contacts network.
the liquid phase. The interphase mass transfer rate is No heat exchange with the surroundings of the
described in terms of the two-film model: reactor has to be accounted for, since hydroprocessing

rG
N i = K --
Hi
C.
,) with
1
-=-+-
KL
1
kGHi
1
kL

The interphase mass transfer flux is calculated for each


(2)
reactors are operated adiabatically. Three energy equa-
tions are considered, one for each phase. The catalyst
particles are assumed to be isothermal. The energy
transfer between the gas phase and the liquid phase is
made up of a conductive heat flux and a convective
contribution due to the transport of enthalpy by the
component of the mixture. interphase mass transfer. The energy equation for the
Shah et al. (1978) considered deviations from plug gas phase is
flow in the liquid phase not to be important in most
commercial trickle bed reactors, in contrast with labora-
tory trickle flow reactors. The criterion of Mears (1971)
for isothermal trickle flow reactors was used to estimate
the importance of axial dispersion in the liquid phase. N
Mears criterion sets a bed length below which axial
dispersion effects may be significant. This minimum
bed length is given by
atz=O TG = TGo
2 0 d p CiL0
2 .
min
=- In - (3) The partial molar enthalpy of component i at the gas-
pea, ce liquid interface is considered to be the gas phase partial
molar enthalpy at the interface temperature TI,since
The Peclet number has been correlated to the liquid the heat of vaporization and condensation is accounted
phase Reynolds number, under trickle flow conditions, for in the liquid phase equation. For the liquid-solid
by Hochman and Effron (1969). For typical conditions heat transfer a convective transfer term is considered.
in a HDS reactor, M e a d criterion is well satisfied, so The energy equation for the liquid phase is written
that dispersion effects in the liquid phase do not have
to be accounted for as far as predicted exit values are dTL
concerned. The influence of liquid wall flow can also u,LeLC,L -= hpv(Ts- TL) + hLa;(TI - TL) +
be neglected, since the ratio of reactor diameter to dz
particle diameter is greater than 1000. The liquid phase N
contacts the gas phase and the solid phase, which is CN,a;(Mi, + cPiL(TI- TL)) (8)
reflected in the continuity equations for the reacting i=l
species by two terms, accounting respectively for the
liquid-solid and the gas-liquid interphase mass trans- atz=O TL = TLo
fer:
and for the solid phase is
1 @iL -
Qdz k,uv(C;s- CiL) K a Hi+ e&
N,
rljrj(C~,,...,TS)(-Mj)
= hp,(T, - TL) (9)
i = 1, ...,N (4) j=l

The two-phase pressure drop is expressed in terms of


the single-phase flow pressure drops (BG and BL),
calculated from the Ergun equation (Larkins et al.,
The model accounts for concentration gradients inside 1961).
the catalyst particles, where the reactions take place.
The pores are considered to be completely filled with
liquid. The continuity equation for component i inside (10)
a spherical catalyst is written
where b= 0.416
0.666 + (logl,,(m))2

with boundary conditions: atz=O Pt =PtO


Rate Equations. In the example to follow, ben-
at[=O zothiophene, dihydrobenzothiophene,dibenzothiophene,
and 4,6-dimethyldibenzothiophenewere chosen as sul-
fur components. A set of rate equations, describing the
dP hydrodesulfurization of benzothiophene in the liquid
at =- K,u,(C~~
- CiL)= phase by a CoMo catalyst supported on alumina, was
2 developed by Pille and Froment (1994). Benzothiophene
N,
(BT)is desulfurized in ethylbenzene in two ways, direct
hydrogenolysis and hydrogenation t o dihydrobenzo-
thiophene (DHBT), followed by hydrogenolysis to ethyl-
Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994 2977
benzene (EB). The rate equations are A1203 catalyst is described by the kinetic equation of
Miller and Hineman (1984).
The rate equations mentioned above do not account
for the competitive adsorption of other sulfur compo-
nents or hydrocarbons.

Estimation of the Physical Properties


The critical temperature, critical pressure, heat of
formation, Gibbs free energy of formation, and ideal gas
heat capacity, which are required for the calculation of
various physical data, were taken from the literature.
Group contribution methods were used when specific
values were not available. The acentric factor was
calculated by means of the Lee-Kesler method (Lee and
At 533 K, for example, the parameters take on the Kesler, 1975). Various data like the heats of reaction
following values:
in the liquid phase, the heats of vaporization, the heat
capacity of the gas phase and the liquid phase, the
equilibrium constants of the reactions in the liquid
phase, the densities of gas phase and liquid phase, and
-3 the Henry coeffkients were obtained from calculations
based on the Peng-Robinson equation of state. For
hydrogen and hydrogen sulfide in the liquid phase
binary interaction parameters were used in the Peng-
Robinson equation of state. These were obtained re-
spectively from Moysan et al. (1983) and Graboski and
Daubert (1978b). The viscosity of the gas phase and
the liquid phase was determined with the method of
Brulez and Starling (1984). The thermal conductivity
The rate equations for dibenzothiophene hydrodesulfu- of both phases was calculated using the method of
rization of Broderick and Gates (1981) were modified Chung et al. (1988). The diffusion coefficients were
into the following rate equation for the direct hydro- obtained from the Wilke-Chang method (Wilke and
genolysis: Chang, 1955).
The mass transfer coefficient k ~ a ;a t the liquid side
of the gas-liquid interface was derived from a correla-
tion presented by Sat0 (19721, and the gas side mass
transfer coefficient kw,' at that interface was derived
from Reiss' correlation (1967). The liquid-solid mass
transfer coefficient was obtained from the correlation
of Van Krevelen and Krekels (1948). The heat transfer
coefficients were derived from the mass transfer coef-
with ficients using the Chilton-Colburn analogy (1934).
k , = 7.84 x lo8 exp(-158000/RT) kmol/(kg,,, s)
Integration Method
kDgT,o = 5.31 m3/kmoi KH,,, = 4.02 m 3 h O i
KH,s,o= 1.72 The integration in the axial direction was performed
using a fourth order Runge-Kutta routine with variable
and for the hydrogenation of dibenzothiophene, step size. The intraparticle integration was carried out
with an orthogonal spline collocation method. The
temperature of the solid phase and the surface concen-
trations are unknowns, since resistance to mass and
heat transfer is accounted for at the catalyst surface.
An initial guess has to be made to perform the intra-
with particle integration. The initial guesses are then up-
dated, using a Newton-Raphson method, until the
k , = 4.17 x lo3 exp(-99100/RT) m3/(kgcats) required accuracy is obtained.
K D g T , r = 3.97 x 10 exp(-14100/RT) m3/kmol
Results of the Simulation and Discussion
The hydrodesulfurization rate of 4,6-dimethyldiben-
zothiophene was derived from the desulfurization rate In the example to follow a synthetic feed mixture with
of dibenzothiophene by weighing the latter with the diesel characteristics was chosen, consisting of paraffins,
ratio of the pseudo first order desulfurization rate naphthenes, aromatics, sulfur, and nitrogen compo-
coefficients of 4,6-dimethyldibenzothiopheneand diben- nents. The sulfur content of the feed, 1.82 wt %, had
zothiophene. This ratio is 1/15 a t 573 K (Houalla et al., to be reduced to 0.05 wt %. Benzothiophene, dihy-
1980). drobenzothiophene, dibenzothiophene, and 4,6-dimeth-
Quinoline was chosen as nitrogen component. The yldibenzothiophene were taken as sulfur-containing
hydrodenitrogenation reaction of quinoline (Q) t o n- components and quinoline as the nitrogen-containing
propylcyclohexane (PCH) in the liquid phase on a CoMo/ component.
2978 Ind. Eng. Chem. Res., Vol. 33,No. 12,1994

Table 1. Composition of the Synthetic Diesel Type Feed gas. Thermodynamic equilibrium was assumed be-
feed components composition (mol %) tween the gas and the liquid phase at the reactor inlet.
sulfur components total: 10.4 The reactor geometry, catalyst properties and inlet
Benzothiophene 7.22 conditions are given below as follows.
Dibenzothiophene 2.33 Reactor geometry: diameter, 2.82m; length, 7.625m.
4,6-Dimethyldibenzothiophene 0.831
Dihydrobenzothiophene 0.0281 Catalyst properties: equivalent diameter of a catalyst
nitrogen component total: 1.53 particle, 1.3 x m; porosity of the catalyst, 0.6 mP/
Quinoline 1.53 mp3;bulk density of the bed, 710 kgcaJmr3;density of
paraffins total: 30.0 catalyst, 1420 kg,,Jmp3.
n-Clz 1.13
n-Cls 1.23 Inlet conditions: inlet temperature, gas and liquid
n-Clc 1.79 phase 590 K inlet pressure, 5000 kPa; WIFs, 0.92kgcat
n-Cx 5.71 h/(mol of S); LHSV,3.16 m ~ ~ / ( h); m ~liquid
t ~ flow rate,
n-Cx 5.56 1550 tons/day (1805 m3/day); gas flow rate, 116 tons/
n-Cu 5.07 day (314000 m3 (NTP)/day); total sulfur content, 1.82
n-Cls 4.08
3.02 wt %; nitrogen content, 0.117wt %.
n-C19
n-Czo 2.41 The components of the diesel-type mixture are dis-
naphthenes total: 31.0 tributed over both the liquid phase and the gas phase.
n-propylcyclohexane 0.153 The components in the gas phase are also considered
n-nonylcyclohexane 17.3
cis-decalin 13.5 for the calculation of the sulfur content of the diesel-
aromatics total 27.0 type mixture, while hydrogen sulfide present in the gas
ethylbenzene 0.0282 or liquid phase is not. The evolution of the sulfur
n-nonylbenzene 6.14 content of the diesel-type mixture through the reactor
indene 2.63 is shown in Figure 1. Benzothiophene reacts faster than
indane 5.92 dibenzothiophene. The slowest reaction is the removal
naphthalene 7.27
anthracene 2.72 of the 4,6-dimethyldibenzothiophene. The major frac-
biphenyl 2.32 tion of the sulfur removal takes place in the initial part
cyclohexylbenzene 3.42 10-3 of the reactor, which is reflected in a significant tem-
perature increase. The maximum difference between
Table 2. Composition of the Treat Gas (Recycle + gas and liquid phase temperature amounts to 5 "C close
Make-up Gas)
to the inlet and drops below 0.1 "C at the reactor outlet.
composition The temperature increase between inlet and exit amounts
component (mole fraction) to 27 "C. It should be noted that the hydrogenation
hydrogen 0.618 reactions of aromatic components like naphthalene and
hydrogen sulfide 0.0133 anthracene were not considered. The temperature and
nitrogen 0.0681
ammonia 0.00219 concentration differences between the liquid bulk phase
methane 0.255 and the catalyst surface were found to be negligible. The
ethane 0.0431 evolution of the molar flux of hydrogen in the liquid and
in the gas phase are shown in Figure 2. The molar flux
The composition of the diesel-type feed is given in of hydrogen in the liquid phase that would be in
Table 1, and the composition of the treat gas in Table equilibrium with the molar flux of hydrogen in the gas
2. This treat gas consists of make-up gas and recycle phase is also represented. The liquid phase in the
P P W mole fraction r S
0.08

- 6

I
- 0.07
- 0.06

1 - Total sulfur content - 0.05

4-..-. - 4,6Dimethyldibenzothbphena - 0.04


5- - - Dihydrobenzothlophene
6- Mole fraction YS in the gas phase
o . ~

, - 0.02

- 0.01

- 0
0 2 4 6
Axial position [m]
Figure 1. Axial profile of the sulfur content of the diesel-type mixture and of the mole fraction of H2S in the gas phase.
Ind. Eng. Chem. Res., Vol. 33, No. 12,1994 2979

1 -(FH) Molar flux of hydrogen in the liquid phase


2 . (Q
' ' Molar flux of hydrogen in the liquid phase
if saturated with hydrogen
14 ......
'. ..........
........
3 .................
..... .....................2
'
1 3
-
---- (qGMolar flux of hydrogen in the gas phase
..........................................................
0.75

12 0.5

10 0.25

4
-
------_____
------ --__.___

1 I I
8
0 2 4 6
Axial position [rn]
Figure 2. Axial molar flux profile of hydrogen in both phases.
PPMS mole fraction %S
0.08
18,000

16,000
- 0.06
14,000

12,000
2 Without resistanceto gas-liquid mass transfer
( liquid saturated with hydrogen )
10,000

8,000
- 0.03
6,000

4,000

2,000

0 I I 0
0 2 4 6
Axial position [rn]
Figure 3. Axial profile of the sulfur content of the diesel-type mixture and the mole fraction of HzS in the gas phase.
initial part of the reactor is far from being saturated The intraparticle diffusion limitations are reflected
with hydrogen. The axial profiles of the sulfur content in the values of the effectiveness factors given in Table
of the diesel-type mixture in both cases (liquid saturated 3. These are arrived from the calculated intraparticle
with hydrogen and no saturation) are presented in gradients.
Figure 3. The conversion of the sulfur components is
lower when the resistance to gas-liquid mass transfer Kinetic Modeling of the Hybgenolysis and
is considered, Since the hydrodesulfiuization rates are Hydrogenation ofDibenzothiophene and
favored by higher hydrogen concentrations. Alkyl-SubstitutedDibenzothiophene
In Figure 4 the sulfur content at the reactor exit is
shown as a function of the inlet temperature and Detailed kinetic equations for the conversion of ben-
pressure. Additional catalyst volume, more severe zothiophene (BT) and dibenzothiophene (DBT) were
reaction conditions, or more active catalysts are required mentioned in the section ,on multiphase reactor simula-
if the future specifications have to be satisfied. The tion. They distinguished between a-sites, on which the
removal of nitrogen components is slower than the hydrogenolysis reactions take place and z-sites, on
sulfur removal, as shown in Figure 5. which the hydrogenations take place. They account for
2980 Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994

ppmwS at the reactor exit


1,800

I I I
400
4,000 4,500 6,000 5.500 6,000
Ida- [kpel
Figure 4. Sulfur content of the diesel-type mixture at the reactor exit as a function of temperature and pressure. Initial sulfur content:
1.82 wt %.

PpmwN Mole fraction NH:,


1,180 0.003

1,160 O.OM8

1,140 0.0026

1,120 0.0024

1,100 0.-

...-
1,080
e
.
2
\ 0.002

,/ ,a 1 - Nitrogen content of the diesel type mixture


1,m 0.0018
.
e
.
2 Mole fraction of NHI in the gas phase

1,040 0.0016
2 4 6
Axial position [m]
Figure 5. Axial profile of the nitrogen content of the diesel-type mixture and of the mole fraction of NH3 in the gas phase.
competitive adsorption of H2, H2S, and the other react- dibenzothiophene, for 4-methyldibenzothiophene,for
ing species on both the 0- and t-sites. Two rate 4,6-dimethyldibenzothiophene, for 1,6-dimethyldiben-
equations were used by Broderick and Gates (1981) for zothiophene, and for 1,2,6-trimethyldibenzothiophene
the conversion of DBT, containing a total of six kinetic are shown in Figures 6, 7, 8, 9, and 10, respectively.
and adsorption coefficients. There are 215 rate equations for hydrogenolysis and
What if the oil fraction contains not only DBT, but 282 rate equations for the hydrogenations in the reac-
all mono-, di-, and trisubstituted DBT? Is it possible tion networks of DBT and mono-, di-, and trisubstituted
to maintain a Hougen-Watson approach accounting for DBT. As shown in Table 4, these rate equations contain
the adsorption of the species in that case? It is possible 497 kinetic coefficients and 636 adsorption equilibrium
to account for the complete reaction network of each constants.
sulfur-containing feed component? For each substituted DBT (s-DBT), one adsorption
The problem will be illustrated for the hydrogenolysis equilibrium constant on the a-sites, K D B Tand
, ~ , one rate
and hydrogenation of DBT and the methyl-substituted coefficient for the hydrogenolysis into biphenyl, ~ D B T , ~ ,
DBT. have to be considered. This leads to 44 different
Reaction Networks and Kinetic Modeling at the adsorption equilibrium constants for substituted DBT
Molecular Level. The complete reaction network for and 44 rate coefficients for substituted DBT hydro-
Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994 2981
Table 3. Values of Effectiveness Factors for the Various
Reactionsa
axial position (m)
reaction 0 1 2
DBT-BPH 0.23 0.91 0.94
DBT-CHB 0.55 0.93 0.94
DMDBT-DMBPH 0.36 0.92 0.97
DMDBT-DMCHB 0.56 0.94 0.98
BT-DHBT 0.31 0.44
BT-EB 0.37 0.44
DHBT-EB 9.9 0.63
Q-PB 1 1 1
DBT, dibenzothiophene; BPH, biphenyl; CHB, cyclohexylben-
zene; DMDBT, 4,6-dimethyldibenzothiophene; DMBPH, 4,4'-di-
methylbiphenyl; DMCHB, 4,6-dimethylcyclohexylbenzene;BT,
benzothiophene; DHBT, dihydrobenzothiophene; EB, ethylben-
zene; Q, quinoline; PB, propylbenzene.

THDBT

Figure 7. &action network for HDS of 4-methyldibenzothiophene.

CHB

it

BCH
Figure 6. Reaction network for HDS of dibenzothiophene.

genolysis. Hydrogenolysis of the 44 substituted DBT


leads to only 29 different substituted biphenyl mol-
ecules, due to rotation of the phenyl rings in biphenyl
with respect to each other (Streitwieser and Heathcock,
1985). Consequently, 29 adsorption equilibrium con-
stants for substituted biphenyl (s-BPH) on the 0-sites,
KBPH,,,,have to be retained. it
For each substituted DBT, one adsorption equilibrium
constant on the t-sites, KDBT,~, is required, which leads
to 44 different adsorption equilibrium constants for
substituted DBT on the t-sites. Hydrogenation of each
of the 4 monosubstituted DBT, of each of the 12 Figure 8. Reaction network for HDS of 4,6-dimethyldiben-
zothiophene.
nonsymmetrical disubstituted DBT, and of each of the
24 trisubstituted DBT leads to two different substituted rium constants for the resulting product substituted
tetrahydrodibenzothiophene(s-THDBT)molecules. Hy- tetrahydrodibenzothiophene,KTHDBT,~, have to be evalu-
drogenation of each of the four symmetrical disubsti- ated.
tuted DBT results in one type of tetrahydrodiben- Also, 84 rate coefficients for the further hydrogenation
zothiophene molecules. Consequently, 84 (4 x 2 12 + of substituted tetrahydrodibenzothiophene into substi-
+ +
x 2 24 x 2 4) rate coefficients for the hydrogenation tuted hexahydrodibenzothiophene (s-HHDBT),k T m B T , r ,
of substituted DBT, ~ D B T , ~and
, 84 adsorption equilib- as well as 84 adsorption equilibrium constants for the
2982 Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994

Table 4. Total Number of Parameters for the


Hydrosulfurization of Dibenzothiophene and
Methyl-Substituted Dibenzothiophene: Molecular
Approach
a-Sites
adsorption (s)-DBT KDBT,dm;n;P) 44 1 +
hydrogenolysis (s)-DBT kDBT,dm;nP) 44 + 1
adsorption (s)-BPH KBPH,dm;nP) 29 1 +
adsorption (s)-THDBT KmBT,dm;np) 84 + 1
hydrogenolysis (S)-THDBT kTHDBT,dm;n;p) 84 4- 1
adsorption (s)-HHDBT K"DBT,dm;n;P) 84 f 1
hydrogenolysis (s)-"DBT kmDBT,dm;n;p) 84 + 1
adsorption (s)-CHB Kcm,dm;n;p) 55 + 1
adsorption HZ KHZP 1
adsorption H2S KH~s,~ 1
5-Sites
adsorption (s)-DBT KDBT,,(m;nP) 44 1 +
hydrogenation (s)-DBT kDBT,r(m 84 1 +
adsorption (SI-THDBT KTHDBT,r(m;n;P) 84 + 1
hydrogenation (s)-THDBT kTHDBT,r(m;n;p) 84 + 1
adsorption (s)-HHDBT KHHDBT,r(m;n;p) 84 + 1
adsorption (s)-BPH KBpH,r(m;n;PI 29 + 1
hydrogenatin (s)-BPH kBw,r(m;nP) 55 + 1
adsorption (s)-CHB KCHB,r(m;n;P) 55 1 +
hydrogenation (s)-CHB kcm,,(m;n;p) 55 + 1
adsorption (s)-BCH KBcH,,(m;n;p) 29 + 1
adsorption Hz KH2.r 1
adsorption H2S KH~s,~ 1
total 1133

For each of the 84 substituted tetrahydrodiben-


zothiophenes, one adsorption equilibrium constant on
the a-sites, KTHDBT,~, and one rate coefficient for the
hydrogenolysis into substituted cyclohexylbenzene,
Figure 9. Reaction network for HDS of 1,6-dimethyldiben-
zothiophene . KTHDBT,~, have t o be introduced. Hydrogenolysis of the
84 substituted tetrahydrodibenzothiophenes leads to
only 55 different substituted cyclohexylbenzene mol-
ecules, due to rotation of the phenyl and cyclohexyl rings
in cyclohexylbenzene with respect to each other. Con-
sequently, 55 adsorption equilibrium constants for
substituted cyclohexylbenzene (s-CHB) on the a-sites,
K C H B ,have
~ , to be retained. Also, for each of the 84
substituted hexahydrodibenzothiophenes, one adsorp-
tion equilibrium constant on the a-sites, KHHDBT,~, and
one rate coefficient for the hydrogenolysis into substi-
tuted cyclohexylbenzene, ~ H H D B T , ~have
, to be consid-
ered.
For each of the 29 substituted biphenyls, one adsorp-
tion equilibrium constant on the r-sites, KBPH,~, has t o
be determined. Hydrogenation of each of the 3 mono-
substituted biphenyls, of each of the 8 nonsymmetrical
disubstituted biphenyls, and of each of the 15 trisub-
stituted biphenyls gives two different substituted cy-
clohexylbenzene molecules. Hydrogenation of each of
the three symmetrical disubstituted biphenyls gives one
type of substituted cyclohexylbenzene molecules. Con-
sequently, 55 (3 x 2 + 8 x 2 + 15 x 2 + 3) rate
coefficients for the hydrogenation of substituted biphe-
nyl into substituted cyclohexylbenzene, KBPH,~, and 55
adsorption equilibrium constants for the product sub-
stituted cyclohexylbenzene on the r-sites, KcHB,~, are
introduced.
For each of the 55 substituted cyclohexylbenzenes, one
rate coefficient for the hydrogenation into substituted
bicyclohexyl (s-BCH), K C H B , ~ , has to be considered.
Hydrogenation of the 55 different substituted cyclo-
Figure 10. Reaction network for HDS of 1,2,64rimethyldiben- hexylbenzenes results in only 29 different substituted
zothiophene. bicyclohexyls, so that 29 adsorption equilibrium con-
stants for substituted bicyclohexyl, KBCH,~, have to be
retained.
product substituted hexahydrodibenzothiophene, In addition, for nonsubstituted DBT, one of each of
KHHDBT,~,
have to be considered. the above parameters has to be evaluated. Also adsorp-
Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994 2983
Table 5. Hydrogenolysis Rate Coefficients of Assumption 2: Methyl groups at a distance from the
Thiophene,' Benzothiophene,' and Selected sulfur atom beyond the a-position only exert electronic
Methyl-SubstitutedDibenzothiophened
effects on the adsorption.
Reactant Structure Pseudo-first- Assumption 3: Only methyl groups on the aromatic
order rate constant ring exert an electronic influence.
3
m 1 (kgcat s) Assumption 4: Methyl groups in the 4- and 6-posi-
tions also sterically hinder the adsorption.
thiophene 1.38 x 10- Assumption 6: Once a molecule is adsorbed, only
the electronic effects of the methyl groups are of
importance.
benzothiophene 8.11 X I O - ~ The adsorption equilibrium constants for (substituted)
DBT ((s)-DBT)can then be expressed as follows:
DBT
dibenzothiophene 7.38 x 10-
1-MeDBT

2,Sdlmethyl- 6.72 x 10-


2-MeDBT
dlbenzothlophene 3-MeDBT

3,7-dimethyl- 3.53 x 10-


4-MeDBT
dibenzothlophene

emethyl- 6.64~10-~
1,7-DiMeDBT
dibenzothlophene 1,8-DiMeDBT
1,g-DiMeDBT
4,Mimethyl- 4.92~10.~
2,7-DiMeDBT
dibenzothiophene
2,8-DiMeDBT

a Reaction conditions: 0.25 mol % reactant concentration, 300 3,7-DiMeDBT


"C, 71 atm, CoMo/AlzOs catalyst (Nag et al., 1979). Reaction
conditions: 0.15 mol % reactant concentration, 300 "C, 102 atm, 1,6-DiMeDBT
CoMo/AlzOs catalyst (Houalla et al., 1980).
tion equilibrium constants for H2 and H2S on the a-sites
and the mites have to be determined. This leads t o a 2,6-DiMeDBT
total of 1133 parameters. A kinetic model containing
1133 parameters is clearly unrealistic. A different
approach is required to reduce this number. 3,6-DiMeDBT
Kinetic Modeling Based upon Structural Con-
tributions. What is proposed in this section is to go
beyond the molecular level in the modeling of the 4,6-DiMeDBT
reaction rates. For reactions involving substituted
components, the rates are related whenever possible t o
those of a nonsubstituted reference component in terms 1,2-DiMeDBT
of the influence of the substituents on the adsorption
equilibrium constants and the rate coefficients. 1,3-DiMeDBT
To get some feeling of the influence of the substitu-
ents, Table 5 presents first order rate coefficients for 1,4-DiMeDBT
the hydrogenolysis of various sulfur-containingcompo-
nents in multiphase operation, free of diffusional limita-
tions (Nag et al., 1979; Houalla et al., 1980). It may be 2,3-DiMeDBT
concluded that the position of the methyl substitutents
is more important than their number. This was con- 2,4-DiMeDBT
firmed by the data of Kilanowski et al. (1978).
Effects of Methyl Substituents on the Hydro-
genolysis Reactions. The hydrogenolysis reactions 3,4-DiMeDBT
involve vertical adsorption of the molecules through the
S-atom on the a-sites (Houalla et al., 1978; Kabe et al.,
1993). The assumptions which permit the reduction of
the number of parameters for the hydrogenolysis steps
along the structural contributions approach are as
follows.
Assumption 1: In the adsorption electronic and
steric effects are to be considered separately.
2984 Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994

1,2,8-TriMeDBT with
KELDBT(m;n;p) DBT(m;O;O)
f ~KE L
1,2,g-TriMeDBT
K E L ~ ;n ~ =
~ ;o) ;O
( K~ E L ~ ~;PI~ ( ~

and
1,3,6-TriMeDBT
= KsTDBT(m;4;0)
KsTDBT(4;0;0) = KsTDBT(m;4;p)=
KsTDBT(m;0;6) = K s ~ ~;72~;6)~ ( m
1,3,7-TriMeDBT
KsTDBT(4;0;6)
= KsTDBT(m;4;6)
f KS,DBT(4;0;0) +
1,3,8-TriMeDBT KsTDBT(m;O;6)
with
1,3,9-TriMeDBT n 4, m =e 4 , p f 6
The adsorption equilibrium constants for the various
substituted DBT are related to that of DBT through five
1,4,6-TriMeDBT multiplying factors. Instead of 45 different parameters
in the molecular approach, only 6 parameters appear
in the approach based upon structural contributions:
1,4,7-TriMeDBT KDBT u, K E L ~ ~ ~ ( ~ ; K OE; OL) ~
, ~~(~ K; ~~ ~ ~; ~O~)(,m ; n ; p ) ,
KsTDBT(4; 0;0), and KsFBT(4; 0;6).
The rate coefficient for the hydrogenolysis of (substi-
1,4,8-TriMeDBT tuted) DBT into (substituted) biphenyl ((s)-BPH) de-
pends only on the number of methyl groups. There are
four rate coefficients: KDBT,AO;O;O) for DBT, ~DBT,&;O;O)
1,4,9-TriMeDBT = ~DBT,~(O;O;O) K E L ~ ~ ~ ( ~ ; O ; for O ) mono-Me-DBT,
k~~~,a(m;= n ; ~DBT,~(O;O;O)
O) k~~~~~(m for; di-me-
n;O)
DBT, and k ~ ~ ~ , , , ( m ;=n~DBT,~(O;O;O)
;p) k ~ ~ ~ ~ ~ (for m;n;p)
tri-Me-DBT with k ~ ~ ~ ~ ~ ( fm ~; ~n E; Lp ~) ~ ~ ( and ~ ; O ; O )
2,3,6-TriMeDBT
~ D B T , A ~ ; ~=; O~)D B T , A ~ ; O ; ~ ) .
The adsorption equilibrium constant for the product
(substituted) biphenyl on the a-sites is assumed to
2,3,7-TriMeDBT depend only on the total number of methyl groups:
KB~H,,,(O;O;O) for biphenyl, K ~ p ~ , , , ( m ; 0=; 0K~p~,J0;0;0)
)
KEL+&~H(~;O;O) for monomethylbiphenyl, K~p~,o(m;n;O)
2,3,8-TriMeDBT = KBPH,AO;O;O) K E L + S T ~ ' ~ ( ~for
; ~dimethylbiphenyl,
;O)
and K ~ p ~ , o ( m ; n=; pKBPH,,,(O;O;O)
) K E L + S T ~ ~ ~for( ~ ; ~ ; P )
trimethylbiphenyl with K~p~,o(m;n;O) = K~p~,dm;O;p).
2,3,9-TriMeDBT Tetrahydrodibenzothiophenecontains a benzene ring
and a thiophenic ring. For the hydrogenolysis of
substituted tetrahydrodibenzothiophene(s-THDBT), it
2,4,6-TriMeDBT can be assumed that methyl groups in the 7-, 8-, and
9-positions have no influence on the adsorption equi-
librium constant. Methyl groups in the 1-, 2-, and
2,4,7-TriMeDBT 3-positions only have an electronic influence on the
adsorption. Methyl groups in the 6-position only steri-
cally hinder the adsorption through the sulfur atom.
2,4,8-TriMeDBT Methyl groups in the 4-position have an influence on
the adsorption resulting from both electronic effects and
steric hindrance. The steric hindrance of a methyl
2,4,9-TriMeDBT group in the 4-position, i.e., on the phenyl moiety, is not
the same as that of a methyl group in the 6-position,
which is on a partially hydrogenated phenyl moiety.
Also,
3,4,6-TriMeDBT
K,,THDBT(~.O.O)
9 , = K STTHDBT(m;4;0) =
=
KSTTHDBT(4;O;p) = KsTTHDBT(m;4p)
3,4,7-TriMeDBT
THDBT
KST (4;np) withp f 6 and n # 6
3,4,8-TriMeDBT ,, =
KsTTmBT(O;O;6)= KsTTHDBT(O*6.p)
KS,THDBT(m;O;6)= KsTTHDBT(m;n;6)=
3,4,9-TriMeDBT ~ ~ ~ ~ ~ ~ ~with ~ m( f m4 and
; 6n t
p 4)
= K STTHDBT(m;4;6)
KSTTHDBT(4.0-6)
9 , = KSTTHDBT(4;6;p)
Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994 2986
HHDBT
KEL (m;n;O)= KELHHDBT(m;np) with m =
and 1 , 2 , 3 ; p = 6, 7 , 8 , 9 and n m
KELTHDBT(m;O;O)
= KEL THDBT(m;O;p) Instead of 85 parameters, only 6 parameters have to
be determined: KHHDBT,~,K E L " ~ ~ ~ ( ~ ; O ; O ) ,
with m = 1 , 2 , 3, 4 a n d p = 6, 7 , 8 , 9 KELHHDBT(m;n; 01, 4;0;01, 0;0;61, and
KsFBT(4;0;6).
K E , T ~ ~ ~ ~ ( T T=z ;KEL
o ; oTHDBT
) (m;n;p) The rate coefficient for the hydrogenolysis of (substi-
tuted) hexahydrodibenzothiophene into (substituted)
with m = 1 , 2 , 3 , 4 ; n = 6 , 7 , 8 a n d p > n cyclohexylbenzene depends only on the number of
THDBT THDBT methyl groups on the aromatic ring: ~HHDBT,~O;O;O),
KEL (m;n;O) = K E L (m;n;p) ~ H H D B T , ~ ~ ; O ; O=) KHHDBT,~(O;O;O)~ E L ~ ~ ~ ~ ( ~ and ; O ; O ) ,
with m = 1 , 2 , 3;p = 6, 7, 8 , 9 and n > m ~ H H D B T , ~ ;= ~ ;~HHDBT,JO;O;O)
~ ) k~~~~~~(m;n;O).
The adsorption constant for (substituted) cyclohexyl-
The approach reduces the number of parameters from benzene on the m i t e s , KcHB,,,, depends on the number
85 t o 6: KwBT,,,, K E L ~ ~ ~ ~ ~ (KELTHDBT(m;n;O),~;O;O), of methyl groups on the phenyl moiety and the cyclo-
K s ~ ~ ~ ~ ~ ( 4K; 0~ ;T0~) ~ , ~ ~ ~and ( OK; sO~ ~; "~~)~,( 4 ; 0 ; 6 ) . hexyl moiety. Consequently, eight different parameters
For the rate coefficient for the hydrogenolysis of have to be retained.
(substituted) tetrahydrodibenzothiophene into (substi- In total there are 215 hydrogenolysis rate equations
tuted) cyclohexylbenzene ((s)-CHB),only the number of with 42 parameters which need to be determined from
methyl groups on the aromatic ring has to be consid- experimental data.
ered: kTHDBT,u(O;O;O),~ T H D B T , ~ ~ ; O ; = O ) ~THDBT,u(O;O;O) Effects of Methyl Substituents on the Hydroge-
; O ;~ TO H) D, B T , A ~ ; ~ ; =
~ E L ~ ~ ~ ~ ( ~ and O ) KTHDBT,AO;O;O) nations. Hydrogenation reactions involve flat adsorp-
k~~l"D"(m;n;O). tion of the molecules on the z-sites of the catalyst
(Houalla et al., 1978; Kilanowski et al., 1978; Kabe et
The same has t o be done for the hydrogenolysis of al., 1993). This suggests the following assumption:
(substituted) hexahydrodibenzothiophene ((s)-HHDBT), Assumption 6: Only the number of substituents and
which has only one benzene ring. Only methyl sub- not their position relative to the sulfur atom has to be
stituents on this ring are considered to have an elec- taken into account for the adsorption on the r-sites and
tronic influence. Consequently, for the hydrogenolysis for the reaction between adsorbed species.
of substituted hexahydrodibenzothiophene, it may be Assumption 6 leads t o four adsorption equilibrium
assumed that methyl groups in the 7-, 8-, and 9-posi- constants for the (substituted) DBT ((SI-DBT):
tions have no influence on the adsorption equilibrium KDBT,,(O;O;O) for DBT itself, KDBT,,(~;O;O) = KDBT,,(O;O;O)
constant for hexahydrodibenzothiophene. Methyl groups K E L + s T ~ ~ ~ ( ~for ; O mono-Me-DBT,
;O) KDBT,r(m;n;O) =
in the 1-, 2-, and 3-positions only have an electronic KDBTJO;O;O)K E L + s T ~ ~ ~ (for ~ ; ~di-me-DBT,
;O) and
influence on the adsorption. Methyl groups in the K D B T , , ~ ;=~KDBT,,(O;O;O)
;~) K E L + s T ~ ~for ~ (tri-
~;~;~)
6-position only sterically hinder the adsorption through Me-DBT. Assumption 6 also leads to four rate coef-
the sulfur atom. Methyl groups in the 4-position have ficients for the hydrogenation of (substituted)DBT into
an influence on the adsorption, due to electronic effects (substituted) tetrahydrodibenzothiophene ((SI-THDBT:
as well as steric hindrance. ~DBT,~(O;O;O)for DBT itself, k ~ ~ ~ , , ( m ;=o kDBT,r(O;O;O) ;o)
kELDBT(m;O;O)for mono-Me-DBT, ~ D B T , , ( ~ ; ~ ; O = )
Again, the steric hindrance of a methyl group in the kDBT,r(O;O;O) k ~ ~ ~ ~ ~ ( m for ; n ; di-Me-DBT,
O) and
4-position, i.e., on a phenyl moiety, is not the same as k ~ ~ ~ , , ( m ;= n ;~DBT,~(O;O;O)
p) k~~~~~(m for; n
tri-Me-
;p)
that of a methyl group in the 6-position which is on a DBT with k ~ ~ ~ ~ ~ ( m#; n ~; ~p E) L ~ ~ ~ ( ~ and ; O ; O )
cyclohexyl moiety. Also, k ~ ~ ~ , , ( r n ; n=; kO~) ~ ~ , ~ ( m ;Eight 0 ; p adsorption
). equilib-
rium constants for (substituted) tetrahydrodiben-
KSTHHDBT(4;0;0)
= KSTHHDBT(m.4.0)
7 , = zothiophene, KTmBT,?,are considered, depending on the
KST
HHDBT
(4;');~)= KST "DBT(m.4.P)
9 ,
= methyl groups on the phenyl moiety and the partially
HHDBT hydrogenated phenyl moiety.
KST (4;np) withpg6andnt6 The rate coefficient for the further hydrogenation of
(substituted) tetrahydrodibenzothiophene into (substi-
= K s T " ~ ~ ~ (9 O, * ~=* P )
KSTHHDBT(0;O;6) tuted) hexahydrodibenzothiophene ((s)-HHDBT) de-
~ ~= ~K s( T " ~ ~m;n;6)
K s T ~m ;0;6) ~( = pends on the number of methyl groups on the aromatic
ring: kTHDBT,r(O;O;O), kTHDBT,r(m;O;O) = kTHDBT,r(O;O;O)
KSTHHDBT(m;6;p)with m t 4 and n t 4 kELTHDBT(m;O;O),and kTHDBT,r(m;n;O) = kTHDBT,r(O;O;O)
= K ST"DBT(m;4;6) =
"DBT(4*0-6)
9 ,
kELTHDBT(rn;n;O)*
KST The adsorption equilibrium constant for (substituted)
Ks~"~~~(4;6;p) hexahydrodibenzothiophene depends on the number of
methyl groups on the phenyl moiety and the cyclohexyl
* KSTHHDBT(4;0;0)
KSTHHDBT(4;0;6) + moiety. Eight different adsorption equilibrium con-
,,
KSTHHDBT(0.0*6) stants have to be considered.
Biphenyl (BPH) consists of two phenyl moieties. It
and is first hydrogenated into cyclohexylbenzene (CHB). The
KELHHDBT(m;O;O)
= KEL HHDBT(m;O;p) adsorption equilibrium constant for (substituted) biphe-
nyl ((s)-BPH),KBPH,,,depends on the total number of
with m = 1 , 2 , 3 , 4 a n d p = 6, 7, 8 , 9 methyl substituents. Therefore, four adsorption equi-
KELHHDBT(m;0;o)
= KEL THDBT(m;n;p) librium constants are considered: KBPH,~(O;O;O) for bi-
phenyl, KBpH,r(m;O;O)z KBHP,r(O;O;O)KEL+STBPH(m;O;O)
with m = 1 , 2 , 3 , 4 ; n = 6, 7 , 8 a n d p > n for monomethylbiphenyl, KBpH,r(m;n;O)= KBPH,r(o;o;o)
2986 Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994

KEL+sT~~(~;~;O)
for dimethylbiphenyl, and Table 6. Total Number of Parameters for the
KBPH,,(~= ; ~KBPH,~(O;O;O)
;~) K E L + s T ~ ~ (for ~ ; ~ ) Hydrodesulfurization
~ ;tri- of Dibenzothiophene and
Methyl-Substituted Dibenzothiophene: Structural
methylbiphenyl with K~p~,~(m;lz;O) = K ~ p ~ , , ( m ; 0 ;In p). Contribution Approach
contrast to the hydrogenation of dibenzothiophene, the
rate coefficient for the hydrogenation of (substituted) a-Sites
biphenyl, ~ B P H , , , only depends on the number of methyl adsorption (s)-DBT KDBT,u(m;n;p) 5+1
groups on the phenyl moiety which undergoes hydro- hydrogenolysis (s)-DBT kDBT,dm;n;P) 3+1
adsorption(s)-BPH KsPH,dm;nP) 3+1
genation. This results in only three rate coefficients for adsorption (s)-THDBT KmBT,dm;n;p) 5+1
the hydrogenation of all biphenyls: k ~ p ~ , ~ ( 0 ; 0 ; 0 ) , hydrogenolysis (s)-THDBT kmBT,dm;np) 2+1
kBPH,r(m;O;O) = k ~ p ~ , , ( o ; o ; O )~ E L ~ ~ ( ~ ; O ; O ) and
, adsorption M-HHDBT KmBT,dm;n;p) 5+1
kBpH,r(m;n;O) = k ~ p ~ , ~ ( o ; OkELBPH(m;rt;O).
;o) hydrogenolysis (s)-HHDBT kmBT,dm;np) 2+1
Cyclohexylbenzene consists of one phenyl moiety and adsorption(s)-CHB Kcm,dm;n;p) 7+1
adsorptionH2 KHDP 1
one cyclohexyl moiety. It is hydrogenated into bicyclo- adsorptionH2S KH~s,~ 1
hexyl, which consists of two cyclohexyl moieties. The
adsorption equilibrium constant for (substituted)cyclo- z-Sites
adsorption(s)-DBT KDBT,r(m;n;PI 3+1
hexylbenzene ((s)-CHB),KCm,?,depends on the number hydrogenation (s)-DBT kDBT,dm;n;P) 3+1
of methyl groups on the phenyl moiety as well as on adsorption(s)-THDBT KTHDBT,r(m;n;PI 7+1
the number of substituents on the cyclohexyl moiety. hydrogenation (s)-THDBT kmBT,Am;n;p) 2+1
Eight different adsorption equilibrium constants are adsorption (SI-HHDBT KHHDBT,dm;nP) 7+1
considered. adsorption (s)-BPB KBw,r(m;nP) 3+1
For the rate coefficient for the hydrogenation of hydrogenation (s)-BPH kBPH,z(m;nP) 2+1
adsorption (s)-CHB Kcm,Am;n;p) 7+1
(substituted)cyclohexylbenzene into (substituted)bicy- hydrogenation (s)-CHB kcm,Am;n;p) 2+1
clohexyl ((s)-BCH), ~ c H B , ~only , the number of methyl adsorption (s)-BCH KBCH,r(m;n;p) 3+1
groups on the phenyl moiety is important. Three rate adsorptionHz KHZJ 1
coefficients are considered: kCHB,r(o;o;o), k c ~ ~ , , ( m ; O ; o ) , adsorptionH2S KH~s,~ 1
and ~ c H B , , ( ~ ; ~ ; O ) . total 93
The adsorption equilibrium constant for (substituted)
bicyclohexyl, KBCH,,depends on the total number of provide significant parameter values. Also, of the 93
methyl groups on both moieties. Four adsorption equi- parameters 70 are adsorption equilibrium constants and
librium constants are considered: KBCH,,(O;O;O)for this number could be considerably reduced through
bicyclohexyl, KBCH,,(~;O;O) = KBCH,,(O;O;O) analogies and reasonable simpljfying assumptions. When
KEL+sT~~~(~;O;O) for mono-Me-BCH, KBCH,,(~;~;O) = only the disappearance of the sulfur-containing compo-
KBCH,,(O;O;O)K E L + s T ~ ~ ~for ( ~di-Me-BCH,
; ~ ; O ) and nents, the production of H2S, and the hydrogenation of
K B C H , ~ ~=;KBCH,AO;O;O)
~;~) K ~ ~ + s ? ~ ~ ( m for ; n ;tri-
p) substituted DBT are considered, 215 rate equations for
Me-BCH with &c~,,(m;n;O)= K ~ c ~ , , ( r n ; O ; p ) . hydrogenolysis and 170 rate equations for hydrogena-
In total there are 282 hydrogenation rate equations tion have to be retained. The number of parameters is
containing 51 parameters which need t o be determined then reduced to 71, of which 54 are adsorption equilib-
from experimental data. rium constants. The approach can also be applied t o
nitrogen-containing compounds.
Conclusions
The modeling of HDS reactors still presents a number
Acknowledgment
of serious challenges, associated with the hydrodynam- This work was partly funded by the European Com-
ics, but also with the complex nature of the feed. mission under the Joule program Contract No. JOU2-
Accounting for the thermodynamic properties of such a 0121. V.V. and G.A.D. are also grateful for a contribu-
mixture is not a simple task, even if the basic data are tion from the Center of Excellence Grant awarded to
available or can be estimated. The kinetic aspects of the Laboratorium voor Petrochemische Techniek by the
the transformation of the large number of S- and Belgian Ministry of Science.
N-components is a formidable problem, however, re-
quiring extensive experimentation for each catalyst Nomenclature
retained for the process. The kinetic modeling applied
up to now is not satisfactory as a basis for the more a, = gas-liquid interfacial area per unit reactor volume,
stringent requirements HDS will be facing in the future. mi2/mr3
A new approach is proposed in this paper. Instead of a / = liquid-solid interfacial area per unit reactor volume,
lumping components and reactions, it retains the details mi2/mr3
of the reaction network of every feed component. Two C, = molar concentration of component i, m0Ym3
levels of modeling are discussed. C,G= molar concentration of i in gas bulk, mol/mc3
C,L= molar concentration of i in liquid bulk, m o l / m ~ ~
According to a molecular approach the total number C,, = molar concentration of i inside the solid, mollm?
of parameters of the 215 hydrogenolysis rate equations C:, = molar concentration of fluid reactant i at surface of
and the 282 hydrogenation rate equations for the HDS solid, mol/m?
of the DBT and all substituted DBT networks consid- C ~ G = specific heat of gas phase, J/(kg K)
ered here is 1133 (Table 4). In the structural contribu- c p =~ specific heat of liquid phase, J/(kg K)
tion approach the total number of parameters for all D,, = effective diffusivity of component i for transport in a
the complete networks has been reduced t o 93. All the pseudocontinuum, mp/(q,t s)
parameters for the hydrogenolysis and the hydrogena- d, = equivalent particle diameter, mp
tion reactions are listed in Table 6. This is still a d, = reactor diameter, m,
relatively large number, but the number of responses fc = friction factor
per S-component in the feed is of the order of 9. A F, = molar flow rate of component i, moYs
thoughtfully designed experimental program should h = heat transfer coefficient, J/(m? s K)
Ind. Eng. Chem. Res., Vol. 33, No. 12, 1994 2987
hf = heat transfer coefficient for the film surrounding a H = atomic hydrogen
particle, J/(mi2 s K) HZ= molecular hydrogen
Hi = Henry's law coefficient, partial molar enthalpy of HzS = hydrogen sulfide
species i, m~~bar/mol, or J/mol HHDBT = hexahydrodibenzothiophene
(-AH) = heat of reaction, J/mol i = component i
AHi, = heat of vaporization of species i , J/mol I = interface
k = reaction rate coefficient, moY(kgCats) L = liquid phase
k G = mass transfer coefficient from gas to gas-liquid p = pellet
interface, based on concentration driving force, m ~ ~ / ( m i ~s = inside solid; also superficial velocity
S) THDBT = tetrahydrodibenzothiophene
k~ = mass transfer coefficient from gas-liquid interface z = with respect to the hydrogenation function,
to liquid bulk, based on concentration driving force, m ~ ~ /u = with respect to the hydrogenolysis function
(mi2S)
kl = liquid-solid mass transfer coefficient, m ~ ~ / ( s)
mi~ Superscripts
KA = K-factor of species A or adsorption equilibrium
constant of component A, m ~ ~ / m o l BCH = bicyclohexyl
K,,o = adsorption equilibrium constant of component i on BPH = biphenyl
a-sites, mL3/kmol CHB = cyclohexylbenzene
Ki,r = adsorption equilibrium constant of component i on DBT = dibenzothiophene
mites, mL3flunol IGM = ideal gas mixture
KL = overall mass transfer coefficient in terms of liquid f = at the reactor exit
concentration gradient, m ~ ~ / ( s)mi~ HHDBT = hexahydrodibenzothiophene
Mi = molecular mass of species i, kg/mol ' = at the reactor inlet; also pure component
N = number of species s = condition at external surface
N , = number of reactions THDBT = tetrahydrodibenzothiophene
N, = rate of transfer of i from the gas bulk to the liquid
bulk, mol/(mi2s) Literature Cited
n = reaction order
Broderick, D. H.; Gates, B. C. Hydrogenolysis and Hydrogenation
pt = total pressure, Pa of Dibenzothiophene Catalyzed by Sulfided COO-Moody-
q = heat flux, J/mi2 s Al203: The Reaction Kinetics. AZChE J . 1981,27,663.
r, = reaction rate of reactionj per unit catalyst mass for BrulB, M. R.; Starling, K. E. Thermophysical Properties of Complex
heterogeneous reaction, mol/(kgcats) Systems: Applications of Multiproperty Analysis. Znd. Eng.
R = gas law constant, J/(mol K) Chem. Process Des. Deu. 1984,23,833.
ReG = Reynolds number for the gas phase, d,G/pG Chilton, T. H.; Colburn, A. P. Mass transfer (absorption) coef-
ReL = Reynolds number for the liquid phase, d&/pL ficients. Prediction from data on heat transfer and fluid friction.
S = stoichiometric coefficient matrix; sb,i] is the stoichio- Ind. Eng. Chem. 1934,26,1183.
metric coefficient of component i in reactionj Chung, T.; Ajlan, M.; Lee, L. L.; Starling, K. E. Generalized
Multiparameter Correlation for Nonpolar and Polar Fluid
T = absolute temperature, K Transport Properties. Znd. Eng. Chem. Res. 1988,27,671.
U,G = superficial gas velocity, r n ~ ~ / ( s)
m,~ Froment, G. F.; Bischoff, K. B. Chemical Reactor Analysis and
u L= l ~superficial liquid velocity, m ~ ~ / ( m
s) ? Design, 2nd ed.; J. Wiley: New York, 1990.
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