Chemical Engineering Science 59 (2004) 2821 – 2829

www.elsevier.com/locate/ces

Deep desulfurization of diesel oil: kinetic studies and

process-improvement by the use of a two-phase reactor
with pre-saturator
C. Schmitz, L. Datsevitch, A. Jess∗
Department of Chemical Engineering, University Bayreuth, Universitatstr. 30, Bayreuth 95447, Germany
Received 3 December 2003; received in revised form 17 February 2004; accepted 24 March 2004

Abstract

Desulfurization of liquid fuels is usually obtained by heterogeneous catalyzed hydrodesulfurization (HDS). Improvement of this process
is needed, particularly with respect to future low residual S-contents of about 10 ppm. Up to now HDS of diesel oil is performed in a
trickle bed reactor equipped with an expensive H2 -recycle, although the H2 -supply is far beyond the amount chemically consumed, at
least for deep HDS of an already hydrotreated feed. In addition, scale up of trickle bed reactors is in general problematic. In this work
kinetic studies and above all a new HDS-concept using a two-phase reactor is presented. Thereby the oil is externally pre-saturated with
H2 and only the liquid phase is passed over the catalytic :xed bed. The H2 -recycle is then redundant, the intrinsic reaction rate can be
utilized, and scale-up problems do not occur. In addition, this concept can also be used for HDS of oils with a higher content of sulfur
and/or unsaturated hydrocarbons by installing a liquid recycle.
? 2004 Elsevier Ltd. All rights reserved.

Keywords: Fuel; Kinetics; Multiphase reactors; Reaction engineering; Desulfurization; Pre-saturation

1. Introduction
In recent years deep desulfurization of diesel oil has at-
tracted much attention due to the gradually reduction of the
statutory sulfur content (Table 1). In 2005, the S-limit will
be reduced e.g. in Europe to 50 ppm compared to today’s
value of typically 350 ppm. (In this paper, the S-content is
given in ppm by weight.) Fuels with even less sulfur are or
will be on the market due to tax bene:ts.
The main reasons for these future stringent S-limits both
for gasoline and diesel oil are: (1) Exhaust gases that con-
tain SOx cause air pollution and acid rain, although e.g.
in western countries transportation fuels only contribute to
about 3% to the total SOx -emissions; nevertheless, ultra-low
sulfur fuels (¡ 10 ppm S) are still needed for urban areas.
(2) For gasoline, a S-content of preferably less than 10 ppm
is needed for new lean fuel engines in combination with
S-sensitive DeNOx-storage catalysts for further reduction of
∗ Corresponding author. Tel.: +49-921-55-74 30;
fax: +49-921-55-74 35.
E-mail address: jess@uni-bayreuth.de (A. Jess).
CO and NOx . (3) The situation is similar for diesel oil with
respect to new catalysts and :lters to reduce particle emis-
sions. (4) New technologies based on fuel cells both for
vehicles and stationary systems need fuels with less than at
least 10 ppm S.
As a quintessence one can state, that by 2010 the S-limit
of transportation fuels will probably be equal or lower than
10 ppm, at least in Europe, Japan and in the USA (Table 1).
Desulfurization is up to now obtained by heterogeneous
catalyzed hydrodesulfurization (HDS), whereby the organic
sulfur species are converted to H2 S and the corresponding
hydrocarbons. H2 S is easily removed from the desulfurized
oil and subsequently converted to elementary sulfur in the
Claus-process. Technically, HDS of diesel oil or of higher
boiling crude oil fractions is up to now performed in a
trickle bed reactor, i.e. in a three-phase system with gaseous
H2 , liquid oil and a solid catalyst. Typical reaction condi-
tions are 350◦ C and 7 MPa. With respect to the increasing
demand for practically S-free fuels (¡ 10 ppm), S-species
with a very low reactivity like dibenzothiophene deriva-
tives (Fig. 1) have to be converted, e.g. in a 2nd stage deep
HDS step, which leads to additional high investment and
operating costs.

0009-2509/$ - see front matter ? 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.03.015
2822 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829
Table 1
Limits of sulfur-content of diesel oil in Europe, Japan and in the USA in ppm (by weight).
1953 1976 1990 1992
EU — — — 500
Japan 12000 5000 — 2000
USA — — 500 — —
a Proposal of EU commission.
S S
Dibenzothiophene 4-Methyl-dibenzothiophene
(DBT) (4-MDBT)
S S
4,6-Dimethyl-dibenzothiophene 2,4,6-Trimethyl-dibenzothiophene
(4,6-DMDBT) (a typical C3-DBT)
Fig. 1. Typical organic sulfur compounds remaining in hydrotreated
(pre-desulfurized) diesel oil (for comparison, see also Fig. 8).
Trickle bed reactors have the following problems: (1)
They are in general complicate with respect to the mass
transfer (gas–liquid and liquid–solid). In addition, proper
hydrodynamic conditions (wetting of catalyst, distribution
of gas and liquid phase) are hard to realize. Scale-up is there-
fore not an easy task and pilot plants are often still needed.
(2) The amount of H2 fed to the reactor—above all in case of
a 2nd stage deep desulfurization of an already hydrotreated
fuel—is much higher than the amount chemically needed
(see below). Therefore, a costly recycle compressor for the
(unconsumed) hydrogen has to be installed.
There are several options to improve (deep) desulfuriza-
tion of fuels: (1) Better catalysts for deep HDS based on
nobel metals are on the market and still the focus of research
(e.g. Fujikawa et al., 2001; Navarro et al., 1996; Reinhoudt
et al., 1999; Robinson et al., 1999). (2) Alternative processes
have been developed like the adsorption process SZorb of
ConocoPhillips (Sughrue, 2003), and (3) extraction of or-
ganic S-compounds by novel extraction media like ionic liq-
uids is now also considered (BIosmann et al., 2001; Esser
et al., 2003).
This work presents a new concept for deep HDS based
on a two-phase :xed bed reactor with pre-saturation of the
oil (Datsevich and Mukhortov, 1997; Schmitz et al., 2003;
Schmitz, 2003).
Although several kinetic studies on HDS with diJerent
catalysts (mainly CoMo and NiMo) were already published
(e.g. Houalla et al., 1980; Zhang et al., 1996), they strongly
diJer with respect to the kinetic parameters obtained (activa-
1996 1997 2000 2005 2006 2011a
— 350 50 — 10
— 500 — 50 — —
— — — 15 —
tion energies, reaction orders etc.). It was therefore also nec-
essary within this study to determine the exact reaction rate
parameters for the commercial CoMo-catalyst used, thereby
excluding all mass transfer resistances (e.g. pore diJusion).
Based on the respective kinetic studies, the intrinsic (maxi-
mum) rate of the chemical reaction of HDS could be deter-
mined and :nally compared with the performance both of
the new two-phase reactor and of the classical trickle bed
reactor.
2. New concept for (deep) desulfurization
The new concept for desulfurization by a two-phase re-
actor with pre-saturator is shown in Fig. 2. At :rst, the oil
is externally saturated with hydrogen in a pre-saturator, and
so only the saturated liquid oil is passed over the :xed bed.
The desired H2 -concentration at the reactor inlet and outlet
is adjusted by the pressure and—if needed(which is not the
case for deep HDS)—by a partial recirculation of the liquid
product. This process is more economic than the classical
trickle bed HDS-technology: (1) Only the oil/hydrogen so-
lution is fed to a two-phase plug Low reactor packed with the
catalyst, where the (dissolved) H2 and the organic S-species
react. Therefore, large three-phase trickle bed reactors can
be replaced by smaller tubular reactors. (2) H2 -recirculation
becomes redundant. (3) Hydrodynamics are simpli:ed, e.g.
a proper distribution of gas and liquid as demanded for a
trickle bed is not needed. So in case of the two-phase con-
cept scale-up problems practically cease to exist.
It should be emphasized, that in case of deep HDS,
the S-content of the already hydrotreated oil is anyway
so low, that independent of the used reactor—trickle bed
or two-phase reactor with pre-saturator—practically no
H2 -depletion occurs along the :xed bed. In other words, a
H2 -supply within the reactor is not needed. This is clearly
proven by Fig. 3, which shows the inLuence of pressure on
the theoretical limit of the initial S-content, where a com-
plete HDS in the two-phase reactor is stoichiometrically
still just possible. For the calculation depicted in Fig. 3,
the following assumptions were made: (1) The solubil-
ity of H2 in diesel oil is according to literature (Ronze
et al., 2002) 0:14 mol H2 per kg of oil and MPa (370◦ C);
almost the same result is obtained for the solubility in
n-dodecane (Schmitz, 2003), used in this work as the base
 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829
Oil (e.g. 100 ppm S)
Pre-saturator
H2
Two phase fixed-
bed reactor
(oil + solid cat.)
Desulfurized oil
Fig. 2. New concept for deep desulfurization by a two-phase reactor with
pre-saturator (the liquid recycle is an option not needed in case of deep
HDS, see text).
5000
2 MPa
(for 100 % conversion by HDS)
Limit of S-content of diesel oil
4000
3000
4600 ppm S
2000
1000
0
0.0 0.5 1.0 1.5
Partial pressure of hydrogen in MPa
Fig. 3. InLuence of H2 -pressure in the pre-saturator on the theoretical limit
of the initial S-content to obtain complete HDS in the two-phase reactor
(process con:g. as in Fig. 2; assumptions see text, e.g. H2 -consumption
by hydrogenation of ole:ns and aromatics is not considered).
component for experiments with model oils. (2) The
H2 -supply only occurs in the pre-saturator, and equilibrium
according to Henry’s law is established. (3) 2 mol H2 are
needed to convert 1 mol S (organic S) to H2 S. Thereby must
be emphasized that this relative low consumption factor is
only valied for CoMo-catalysts with a low hydrogenation
activity (as used in this work); this speci:c point will be
discussed further in Sections 4.1 and 4.4. (4) Ole:ns and
other unsaturated (aromatic) hydrocarbons are not present
(or at least “inert” for hydrogenation on CoMo) in the
pre-desulfurized hydrogenated oil. So a H2 -consumption by
side reactions can be neglected. (5) With respect to kinetics
and an adequate amount of solved H2 within the whole re-
actor, respectively, the minimum H2 -content at the reactor
exit should be at least equivalent to a H2 -pressure of 1 MPa.
For example, in case of a pressure of 3 MPa in
the pre-saturator and an already hydrotreated oil with
2823
500 ppm S, a complete conversion of all S-compounds to
H2 S would only lead to a minor depletion (−7%) of the
dissolved H2 down to a value equivalent to a H2 -pressure
of about 2:8 MPa (Fig. 3). So the amount of H2 leaving the
pre-saturator exceeds many times the amount needed for
100% HDS and would even be adequate to desulfurize an
Recycle pump oil with a much higher initial S-content, according to Fig. 3
4600 ppm S for the assumed pressure of 3 MPa. Only in
case of an oil with a still higher S-content and/or rich in
unsaturates reactive for hydrogenation, an oil recycle would
be needed (see Section 4.4). Nevertheless, even then a liq-
uid recycle is more favourable than a gas recycle as needed
for a trickle bed: The power consumption of a recycle pump
for the liquid is much lower than of a hydrogen recycle
compressor. In addition, the investment costs are higher in
the latter case.
General aspects of the pre-saturation concept were already
presented elsewhere (Datsevich and Mukhortov, 1997), and
discussed in previous publications for the hydrogenation of
(1) n-octene (Battsengel, 2002; Jess et al., 2002), (2) adipic
acid-hexandiole-oligoester (Battsengel et al., 2003), and (3)
ionone (Peter et al., 2003). In all these cases, the concen-
tration of the liquid reactant is in contrast to HDS high, and
therefore a liquid recycle is absolutely needed to reach 100%
conversion.
In the present paper, the pre-saturation concept is ex-
panded to and discussed for deep HDS, i.e. to a typical case
of a low concentration of the liquid reactant. The advan-
tage of the liquid-phase-only hydrogenation for low initial
concentrations is also con:rmed by Stankiewicz (2001), al-
2.0 2.5 3.0 though only based on theoretical considerations without dis-
cussing concrete reactions and experimental data, respec-
tively. The new concept for deep HDS of diesel oil was
tested both for model oils and “real” diesel oils (see also
Schmitz et al., 2003; Schmitz, 2003).
3. Experimental and data analysis
The experiments were carried out in a continuous :xed
bed two-phase reactor (for details see Schmitz, 2003).
The externally heated reactor had a length of 140 cm
and a diameter of 4 mm, resulting in a volume of the
:xed bed of 18 cm3 . The (axial) temperature pro:le was
controlled at four points along the bed, indicating a max-
imum T -diJerence of ±2 K. The oil was pumped to the
pre-saturator, where hydrogen is dispersed into the oil by
means of a frit. The :ll level of oil in the pre-saturator was
controlled and regulated by an inspection glass in combi-
nation with a level controller. From time to time it was
veri:ed, that the oil was really completely saturated with
H2 : A sample of the oil (at reaction conditions) was taken
behind the pre-saturator by a syringe and the amount of
degasing hydrogen was measured.
The oil saturated with H2 in the pre-saturator under re-
action conditions (T; p) was then pumped through the :xed
2824 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829
bed. The total S-content was determined by elementary anal-
ysis (Antek 9000, pyroLuorescence detector) with an error
of about 1 ppm. The calibration was adjusted for a range of
10–300 ppm S.
The content of individual S-species like benzothiophene
(BT), dibenzothiophene (DBT), 4-methyldibenzothiophene
(4-DMDBT) and 4,6-dimethyldibenzothiophene (4,6-
DMDBT) was determined by a S-sensitive gaschromato-
graph (GC Varian CP-3800 with pulsed Lame photometric
detector (PFPD)).
The experiments were conducted with a commercial
CoMo-catalyst (SIud-Chemie C20-6, BET surface area:
245 m2 g−1 ), at H2 -pressures from 1 to 7 MPa, tempera-
tures of 340–400◦ C, and residence times up to 1 g h cm−3
(ratio of mass of catalyst to feed rate of oil). The original
catalyst has a special form of three interlinked cylinders
with a characteristic size of 1:7 mm (equivalent diameter of
spheres with the same ratio of volume to external surface
area). Selected experiments were done with a smaller diam-
eter of 0:2 mm by grinding the original catalyst. (Although
in case of the original catalyst “wall eJects” may contribute
to a decrease of the achieavable conversion, this was not
detected.) Model oils as well as two “real” pre-desulfurized
diesel oils were used as feedstocks. Model oils were ob-
tained by mixing n-dodecane with BT, DBT, 4-MDBT,
and 4,6-DMDBT. The diesel oils with a S-content of 260
and 290 ppm were provided by MiRO re:nery, Karlsruhe,
Germany.
In addition to the experiments with the pre-saturation re-
actor, comparative experiments were also conducted with
a trickle bed reactor (45 cm3 of catalyst), thereby taking a
model diesel oil (300 ppm S as 4,6-DMDBT in n-dodecane)
as a feed.
4. Results and discussion
4.1. HDS of individual S-compounds (experiments with
model oils)
All HDS-experiments were conducted with the two-phase
reactor (except those described in chapter 4.3). Fig. 4 sum-
marizes typical results with model oils (semi-log plot),
whereby each experiment was conducted with only one
single S-species in n-dodecane. (The values in brackets in
): (1)
Fig. 4 indicate slightly insecure results with S-contents less
than 10 ppm, i.e. out of the accurate range of calibration
of the elementary analyser.) As expected, the S-content de-
creases with increasing residence time, although with strong
the residence time (kg s m−3 ). Ac-
diJerences with respect to the reactivity of the investigated
should give a
S-species. Above all, 4,6-DMDBT is much less reactive
than 4-MDBT, DBT, and BT.
The analysis of the HDS product(s) by the S-sensitive
gaschromatograph clearly showed that no S-containing
species other than the model S-compounds of the feed
appeared. So most likely HDS on CoMo exclusively pro-
Fig. 4. HDS of model oils (each) with individual sulfur compounds
(CoMo-catalyst, 360◦ C, 3 MPa, feed: n-dodecane and in each case only
one single S-compound; lines indicate :rst order reaction with respect to
sulfur compound, see text).
ceeds by the so-called direct route under formation of
biphenyl and H2 S without preliminary hydrogenation of the
aromatic ring(s). This is con:rmed by an additional exper-
iment with biphenyl as feed (1% in dodecane). At typical
HDS-conditions (30 bar, 360◦ C, 0:31 g h cm−3 ), a measur-
able conversion of biphenyl—e.g. to cyclohexylbenzene—
was not detected (GC with Lame ionization detector). This
again proves that the CoMo-catalyst used here is relative
inactive for hydrogenation of aromatics. So the assumption
of the relative low consumption ratio of 2 mol H2 per mol S,
as used to compile Fig. 3, is justi:ed for the CoMo-catalyst
used in this work.
All experiments with individual S-compounds show that
the HDS-reaction is :rst order with respect to the investi-
gated compounds. The inLuence of the H2 -pressure is neg-
ligible (zero order), at least in the investigated range from
1 to 7 MPa (Schmitz, 2003). It was beyond the scope of
this study to explain this unexpected reaction order of zero
with respect to H2 . According to literature, this may be ex-
plained by the interplay of H2 -consumption and formation
of HDS-inhibiting H2 S (Vogelaar et al., 2003).
So the decrease of the concentration of individual
S-species is given by
cS = cS; 0 exp(−k1
Thereby cS and cS; 0 are the residual and initial contents
of the S-species (mgS =kgoil = ppm), k1 is the rate constant
(m−3 kg−1 s1 ), and
cording to Eq. (1), the plot of log cS; tot vs.
straight line, which is con:rmed by Fig. 4. The inLuence of
the temperature is given by k1 = k1; 0 exp(−EA =RT).
The kinetic data (reaction order(s), pre-exponential fac-
tors, activation energies) for HDS of DBT, 4-MDBT and
4,6-DMDBT (Table 2) were deduced from experiments with
varied reaction temperature, pressure and initial S-content
 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829 2825

Table 2 1000
Activation energy, pre-exponential factor, and rate constant (360◦ C) for 360°C 380°C
HDS of individual S-compounds (340–400◦ C, 1–7 MPa, CoMo-catalyst

Measured S-content in ppm

(C20-6, SIud Chemie))

S-Compound Experiments (own measurement) 100

+ 20 %
EA in k1; 0 in k1 (360◦ C) in For comparison:
kJ mol−1 cm3 g−1 h−1 cm3 g−1 h−1 EA from
literaturea
10
DBT 87 2:9 × 108 19 92
4-MDBT 117 2:3 × 1010 5 121
4,6-DMDBT 132 2:1 × 1011 2.7 138 - 20 %

a Houalla et al. (1980) 1

1 10 100 1000
Calculated S-content in ppm

Fig. 5. Comparison of measured and calculated residual sulfur contents

(details in Schmitz, 2003). In case of BT, kinetic data were (model oil with 4,6-DMDBT in n-dodecane (300 ppm S); dashed lines
not determined because of its high reactivity, virtually lead- indicate 20% aberration).
ing to full conversion even for low temperatures and/or
residence times (Fig. 4). The values of the activation en-
ergy for the HDS of all three DBT derivatives are in good
agreement with typical data reported in literature (Table 2).
Reruns of experiments with model oil as well as with diesel
oil indicate, that no measurable aging of the catalyst occur
within the investigated timeframe (500 h with diesel oil and
800 h with model oils), and that the reproducibility is very
well.
The inLuence of pore or external diJusion on the ef-
fective rate was excluded by variation of particle size
(model compound DBT; original size of 1.7 and 0:2 mm).
It turned out that for the given conditions, the rate is in-
dependent of the particle size, and so the intrinsic reaction
rate was always measured, at least for the S-compounds
investigated and the original particle size of 1:7 mm. Fur-
ther calculations (Schmitz, 2003) indicate, that e.g. in case
of the relative reactive DBT, pore diJusion would only
have an eJect for a particle size (spheres) of more than Fig. 6. HDS of a model diesel oil consisting of a mixture of 4,6-DMDBT,
about 8 mm. 4-MDBT and DBT in n-dodecane (360◦ C, 3 MPa).
The reliability of the kinetic data is given in Fig. 5 by
the comparison of experimental and predicted values of
the residual S-content based on Eq. (1) and the data given (total) S-contents of less than 300 ppm, competing eJects
in Table 2, taking 4,6-DMDBT as example. The aberra- —e.g. by adsorption phenomena—can be neglected.
tion is about 20%, indicating that the parameters given in Further calculations show that the decrease of the total
Table 2 are satisfyingly describing the conversion of the S-content cS; tot (in ppm) can be well approximated by a rate
model S-compounds within a relative wide range of the second-order with respect to total sulfur, i.e.
S-content from 300 to 10 ppm, i.e. within the adjusted range
of calibration of the elementary analysis (Antek 9000). Sim- cS; tot = cS; tot; 0 =[k2
cS; tot; 0 + 1] (2)
ilar results were obtained for the other S-species (Schmitz,
2003). with the rate constant k2 in m3 kg1 s−1 ppm1 .
The result of HDS of a model oil containing three On :rst hand this is in contrast to the :rst-order reaction
S-species (DBT, 4-MDBT and 4,6-DMDBT (about found for the individual S-species, but this eJect can be
90 ppm S each) with n-dodecane) is shown in Fig. 6. For easily explained by the stepwise HDS of DBT, MDBT and
comparison, calculated results (lines in Fig. 6) based on DMDBT, which strongly diJer in reactivity (see Fig. 4). So
Eq. (1) and the kinetic data (Table 2) are also indicated. It the rate of HDS (with respect to total S) superproportionally
is interesting to note, that the HDS of all three DBT deriva- decreases with increasing degree of desulfurization by the
tives can be well described by the kinetics obtained from increasing portion of the remaining, less reactive compounds
experiments with single S-species. So at least for initial like 4,6-DMDBT.
2826 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829

60
4-MDBT in diesel oil 4,6-DMDBT in diesel oil

(as 4-MDBT or 4,6-DMDBT)

50

S-content in ppm
40
calculated curves for 1st
30 order reaction and the kinetic
data given in Tab.2

20

10

0
0.0 0.2 0.4 0.6 0.8
Residence time τ in g.h.cm-3

Fig. 7. Deep HDS of diesel oil (feed: two already hydrotreated diesel oils Fig. 9. Rest content of selected S-species at diJerent stages of HDS
with 290 and 260 ppm S, 360◦ C, 3 MPa; straight (full) lines indicate of an already hydrotreated (pre-desulfurized) diesel oil (diesel oil with
second order with respect to total S, see Eq. (2)). 260 ppm S, 390◦ C, other conditions as given in Fig. 7; values calculated
based on S-sensitive (PFPD) chromatograms).

4.2. HDS of pre-desulfurized diesel oil

Subsequent to the experiments with model S-compounds,
two “real” pre-desulfurized diesel oils with 260 and
290 ppm S were used as feedstocks for HDS in the
two-phase reactor. Typical experimental results are shown
in Fig. 7 with respect to the inLuence of the residence time
on the total sulfur content. The two straight lines repre-
sent the plot of the linearized form of Eq. (2) (1=cS; tot vs.
The comparison of Fig. 7 with Fig. 6 indicates that the re-
action rate of HDS of both “real” diesel oil (with respect to
total S) is lower than in case of a model oil even with the re-
fractory 4,6-DMDBT, above all in case of the diesel oil with
an initial S-content of 290 ppm S (Fig. 7). Nevertheless,
the conversion rate of individual S-species like 4-MDBT
and 4,6-DMDBT is not or only slightly lower in the diesel
oil matrix, as shown by comparison of measured values in

) to con:rm the second-order reaction of HDS. Fig. 8
shows characteristic S-species determined by chromatog-
raphy (PFPD-detector). As expected, only the refractory
DBT-derivatives are present in the pre-desulfurized feed,
and mainly the multi-substituted S-compounds remain in
the product oil.
the diesel oil (260 ppm S) and the calculation based on the
respective kinetic data of HDS in n-dodecane (Fig. 9). (The
same result is obtained for the second diesel oil, see Schmitz,
2003.) So at least in case of the two investigated diesel oils,
inhibition of HDS by N-compounds (here about 90 ppm N
in both oils) and by aromatic hydrocarbons (not determined

Fig. 8. S-sensitive chromatograms at diJerent stages of HDS of an already hydrotreated (pre-desulfurized) diesel oil (GC with PFPD, feed: diesel oil
with 260 ppm S from MiRO re:nery in Karlsruhe, Germany), 390◦ C, other conditions as given in Fig. 7.
 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829
300
2-phase-reactor
250
S-content in ppm
(as 4,6-DMDBT)
200
Trend 3-phase-
reactor
150
100
50
Trend 2-phase-
reactor
0
0.0 0.2 0.4 0.6 0.8
Residence time τ in g.h.cm-3
Fig. 10. HDS in a conventional trickle bed reactor and in a reactor
with H2 -pre-saturation of oil (model oil with 4,6-DMDBT in n-dodecane,
360◦ C, 3 MPa, SIud-Chemie CoMo-catalyst).
in this work)—as reported in literature (e.g. Koltai et al.,
2002; Ramachandran and Massoth, 1982; Kabe et al., 1997)
—is irrelevant. So the main reason for the relative low reac-
tion rate of the diesel oils (with respect to total S) is there-
fore most probably the high content of C3 - and C4 -DBTs
with three or four additional carbon atoms as methyl- or
ethyl-groups (see Fig. 8), i.e. of S-species, which are obvi-
ously even less reactive than 4,6-DMDBT.
As in case of HDS of the investigated model S-compounds,
the inLuence of the pressure is negligible, at least for the
investigated range from 1 to 7 MPa. The decrease of the
total sulfur content with increasing residence time can be
approximated quite well by assuming a second-order reac-
tion with respect to total sulfur (lines in Fig. 7), which is
in good agreement with the experimental :ndings with a
mixture of model S-compounds. As already expected ac-
cording to the experiments with model oils (with equal or
even higher intrinsic HDS reaction rates), pore or external
diJusion have no inLuence on the eJective rate, which was
again proven by experiments with varied particle size (1.7
and 0:2 mm). So again, the intrinsic rates were measured.
4.3. Comparison of deep HDS in the two-phase reactor
(with pre-saturator) and in a trickle bed reactor
Finally, comparative experiments were also conducted
with a lab-scale trickle bed reactor, thereby using a model oil
with 300 ppm S (as 4,6-DMDBT) in n-dodecane. Compared
to the respective experiment with the two-phase reactor, the
reaction rate is by a factor of about 2.5 lower (Fig. 10).
So only the two-phase reactor with pre-saturator utilizes the
maximum (intrinsic) rate of the chemical reaction. In case
of the trickle bed reactor, this limiting maximum rate is not
reached, probably because of improper gas–liquid distribu-
tion and/or wetting of the catalyst. Thereby must be empha-
sized that probably the operation of the lab-scale trickle bed
reactor could possibly be improved (which was beyond the
2827
Oil (5000 ppm S, 20 wt.-% olefins)
3-phase-reactor
Pre-saturator
H2
Two phase fixed-
Recycle pump
bed reactor (recycle rate: 1.68)
(oil + solid cat.)
Desulfurized oil
1.0 1.2 (10 ppm S, no olefins)
Fig. 11. HDS of a diesel oil rich in sulfur and ole:ns in a two-phase
reactor with H2 -pre-saturation (assumptions see text).
scope of this study), e.g. by adjusting optimal conditions
with respect to the velocity of the liquid and the gas phase.
Nevertheless, a higher reaction rate than the limiting intrin-
sic rate reached with the two-phase reactor is in any case
not possible.
4.4. Outlook: potential extension of the pre-saturation
technology
The two-phase reactor with pre-saturator is by far not
limited to the case of deep HDS, and can easily be ex-
tended to feedstocks rich in sulfur and/or unsaturated hy-
drocarbons. This is illustrated by Fig. 11, taking HDS of
a diesel oil with 5000 ppm S and 20 wt% of unsaturated
hydrocarbons for a simpli:ed, but instructive case study
to underline this suggestion. For the respective calcula-
tion (Fig. 11), the following assumptions were made: (1)
The pressure in the pre-saturator is 5 MPa, i.e. 0:7 mol H2
leave the pre-saturator per kg of oil. (2) For simpli:-
cation, all unsaturated hydrocarbons were considered as
dodecene. (3) The H2 -consumption is 2 mol H2 per mol S
and 1 mol H2 per mol dodecene, respectively. (4) The res-
idence time is suTcient both for complete conversion of
all the ole:ns and to reach a residual S-content of 10 ppm.
(5) A H2 -concentration at the reactor outlet equivalent to
a partial pressure of H2 of 1 MPa is still suTcient with
respect to kinetics.
In contrast to a trickle bed, where hydrogen is supplied by
gas–liquid mass transfer within the reactor, a noticeable de-
pletion of dissolved hydrogen would occur in this case study
within the two-phase reactor. Therefore, a liquid recycle is
needed to compensate the lack of hydrogen. Nevertheless,
the recycle rate of less than two (1.68) needed to ensure the
above-mentioned minimum H2 -content at the reactor outlet
is still relatively small. So the liquid-phase-only hydrotreat-
ing is certainly still more favourable than HDS in a trickle
bed, e.g. with respect to the power consumption of a recycle
gas compressor compared to an oil pump.
2828 C. Schmitz et al. / Chemical Engineering Science 59 (2004) 2821 – 2829
Two aspects should :nally be mentioned:
(1) If other catalysts, e.g. Ni- or Pt-Pd-based systems spe-
ci:c for deep HDS, are used in the second step of HDS, their
hydrogenation properties allow a rather easy hydrogenation
of benzyl rings, and then much more hydrogen than just 2
mol per mol of organic sulfur will be consumed. Neverthe-
less, the basic principle of the pre-saturation concept is still
valid, but a higher total pressure and/or higher recycle rate
of oil would be needed as outlined before.
(2) In contrast to HDS of diesel and fuel oil, the
pre-saturation system has clearly one drawback in case of
HDS of gasoline rich in ole:nes and/or aromatics (e.g. from
Luid catalytic cracking). If a liquid recycle is needed for a
suTcient H2 -supply, the octane number of the product is
presumably decreased, which is not favorable.
So in future experimental work, the extension of the
pre-saturation technology to feedstocks rich in sulfur and/or
unsaturated hydrocarbons by installing a liquid recycle will
have to be further investigated by respective experiments in
order to prove the theoretical suggestions outlined above.
5. Conclusions
A new concept for hydrodesulfurization (HDS) of diesel
oil using a two-phase reactor (pre-saturated oil and solid cat-
alyst) was investigated under typical reaction conditions of
HDS (340–400◦ C, 1–7 MPa, CoMo-catalyst). Model oils
with dibenzothiophene derivatives as well as predesulfur-
ized and therefore hydrogenated diesel oils were used as
feedstocks. On the basis of the experiments and of the out-
lined theoretical considerations, the comparison of HDS in
a classical trickle bed reactor with the new two-phase tech-
nology clearly shows the advantages of the latter: (1) The
new technology utilizes the maximum (intrinsic) chemical
rate of the HDS reaction, whereas in case of a trickle bed
this rate is an upper limit, which can not or only hardly be
reached. (2) The amount of H2 dissolved in the pre-saturator
is by far enough for HDS of already hydrotreated oil. So
there is no need of the presence of gaseous H2 within the
reactor to supply additional H2 into the liquid phase, and a
H2 -recycle is obsolete. (3) The scale-up of the two-phase
reactor is much easier than of a trickle bed reactor. (4) Fur-
thermore, the liquid-phase-only HDS is also an interesting
option for HDS of diesel oils (and other gas oils) rich in
sulfur and/or ole:ns. In this case, a liquid recycle has to be
installed, which is still much less expensive than the com-
mon hydrogen recycle needed for a trickle bed reactor.
Acknowledgements
Financial support by the Deutsche Forschungsgemein-
schaft (Je 257/2) and BP Oil is gratefully acknowledged.
We thank Nick J. Gudde (Re8ning Technology, BP Oil,
Sunbury-on-Thames, Great Britain) for fruitful discussions

and comments, SUDCHEMIE for supplying the catalyst,
and the MiRO re:nery (Karlsruhe) for supplying the diesel
oil samples.
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