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Chemical Engineering Science 59 (2004) 2821 – 2829

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


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

0009-2509/$ - see front matter ? 2004 Elsevier Ltd. All rights reserved.

. Schmitz et al.4. Schmitz. 1953 1976 1990 1992 1996 1997 2000 2005 2006 2011a EU — — — 500 — 350 50 — 10 Japan 12000 5000 — 2000 — 500 — 50 — — USA — — 500 — — — — — 15 — a Proposal of EU commission. In addition. a proper distribution of gas and liquid as demanded for a tion of fuels: (1) Better catalysts for deep HDS based on trickle bed is not needed. Fujikawa et al. or two-phase reactor with pre-saturator—practically no ganic S-compounds by novel extraction media like ionic liq. 1996). that independent of the used reactor—trickle bed ConocoPhillips (Sughrue. 1980. 2001. H2 -depletion occurs along the :xed bed. where a com- on a two-phase :xed bed reactor with pre-saturation of the plete HDS in the two-phase reactor is stoichiometrically oil (Datsevich and Mukhortov. 2003. It was therefore also nec- essary within this study to determine the exact reaction rate S S parameters for the commercial CoMo-catalyst used. product. and Trickle bed reactors have the following problems: (1) so only the saturated liquid oil is passed over the :xed bed. 3. There are several options to improve (deep) desulfuriza. (2) Alternative processes the S-content of the already hydrotreated oil is anyway have been developed like the adsorption process SZorb of so low.. 2001. Dibenzothiophene 4-Methyl-dibenzothiophene (DBT) (4-MDBT) Based on the respective kinetic studies. 2. In other words.g.6-Dimethyl-dibenzothiophene 2. 2003). Reinhoudt It should be emphasized. 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. 1999).. the following assumptions were made: (1) The solubil- Although several kinetic studies on HDS with diJerent ity of H2 in diesel oil is according to literature (Ronze catalysts (mainly CoMo and NiMo) were already published et al.. Zhang et al.. they strongly almost the same result is obtained for the solubility in diJer with respect to the kinetic parameters obtained (activa. S S 4. still just possible. proven by Fig. This is clearly et al. distribution case for deep HDS)—by a partial recirculation of the liquid of gas and liquid phase) are hard to realize. 2002) 0:14 mol H2 per kg of oil and MPa (370◦ C). 2003). et al. 3. This process is more economic than the classical fore not an easy task and pilot plants are often still needed. 8). Schmitz et al. Therefore. 2003). becomes redundant. (2) H2 -recirculation (unconsumed) hydrogen has to be installed. the oil is externally saturated with hydrogen in a pre-saturator. tion energies. and (3) extraction of or.g. 2003). n-dodecane (Schmitz.. Houalla et al. e. Navarro et al. For the calculation depicted in Fig.. Esser H2 -supply within the reactor is not needed. (e.g. 1999. Scale-up is there. thereby excluding all mass transfer resistances (e.). used in this work as the base . trickle bed HDS-technology: (1) Only the oil/hydrogen so- (2) The amount of H2 fed to the reactor—above all in case of lution is fed to a two-phase plug Low reactor packed with the a 2nd stage deep desulfurization of an already hydrotreated catalyst. a uids is now also considered (BIosmann et al. 1. see also Fig. Typical organic sulfur compounds remaining in hydrotreated (pre-desulfurized) diesel oil (for comparison.. (3) Hydrodynamics are simpli:ed... that in case of deep HDS. pore diJusion). which shows the inLuence of pressure on This work presents a new concept for deep HDS based the theoretical limit of the initial S-content. Robinson et al.g. So in case of the two-phase con- nobel metals are on the market and still the focus of research cept scale-up problems practically cease to exist. (e. At :rst.2822 C.6-DMDBT) (a typical C3-DBT) 2. proper is adjusted by the pressure and—if needed(which is not the hydrodynamic conditions (wetting of catalyst.6-Trimethyl-dibenzothiophene (4. 1996. The new concept for desulfurization by a two-phase re- actor with pre-saturator is shown in Fig. New concept for (deep) desulfurization Fig. Japan and in the USA in ppm (by weight). 1997. reaction orders etc. / Chemical Engineering Science 59 (2004) 2821 – 2829 Table 1 Limits of sulfur-content of diesel oil in Europe. They are in general complicate with respect to the mass The desired H2 -concentration at the reactor inlet and outlet transfer (gas–liquid and liquid–solid). large three-phase trickle bed reactors can (see below). where the (dissolved) H2 and the organic S-species fuel—is much higher than the amount chemically needed react. Therefore. a costly recycle compressor for the be replaced by smaller tubular reactors.

/ Chemical Engineering Science 59 (2004) 2821 – 2829 2823 Oil (e.4).0 2. p) was then pumped through the :xed . The new concept for deep HDS of diesel oil was Fig. 2003). e. i. Schmitz et al. (4) Ole:ns and pre-saturator. resulting in a volume of the be emphasized that this relative low consumption factor is :xed bed of 18 cm3 .0 1. 2003). degasing hydrogen was measured. The (axial) temperature pro:le was only valied for CoMo-catalysts with a low hydrogenation controlled at four points along the bed. al- 0. 2. Nevertheless.. 2003. and equilibrium bed two-phase reactor (for details see Schmitz. respec- tively. 2003). 2002). (2) The The experiments were carried out in a continuous :xed H2 -supply only occurs in the pre-saturator. 3. The oil was pumped to the discussed further in Sections 4.5 2. 2.5 3. General aspects of the pre-saturation concept were already presented elsewhere (Datsevich and Mukhortov. 2002. In addition. The :ll level of oil in the pre-saturator was (or at least “inert” for hydrogenation on CoMo) in the controlled and regulated by an inspection glass in combi- pre-desulfurized hydrogenated oil. Thereby must and a diameter of 4 mm. assumptions see text. according to Fig. and (3) 4000 ionone (Peter et al.0 though only based on theoretical considerations without dis- Partial pressure of hydrogen in MPa cussing concrete reactions and experimental data. 2003). InLuence of H2 -pressure in the pre-saturator on the theoretical limit tested both for model oils and “real” diesel oils (see also of the initial S-content to obtain complete HDS in the two-phase reactor (process con:g. 3). that the oil was really completely saturated with and an adequate amount of solved H2 within the whole re.4. the minimum H2 -content at the reactor behind the pre-saturator by a syringe and the amount of exit should be at least equivalent to a H2 -pressure of 1 MPa. by hydrogenation of ole:ns and aromatics is not considered). the investment costs are higher in HDS. 100 ppm S) 500 ppm S. 2000 In the present paper. and 3000 therefore a liquid recycle is absolutely needed to reach 100% 4600 ppm S conversion. indicating a max- activity (as used in this work). the concen- tration of the liquid reactant is in contrast to HDS high. The advan- tage of the liquid-phase-only hydrogenation for low initial 0 concentrations is also con:rmed by Stankiewicz (2001).. For example. and 5000 discussed in previous publications for the hydrogenation of 2 MPa (1) n-octene (Battsengel. in case of a pressure of 3 MPa in The oil saturated with H2 in the pre-saturator under re- the pre-saturator and an already hydrotreated oil with action conditions (T. the pre-saturation concept is ex- panded to and discussed for deep HDS. 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 Two phase fixed- bed reactor Recycle pump oil with a much higher initial S-content. as in Fig.g.. the latter case. where hydrogen is dispersed into the oil by other unsaturated (aromatic) hydrocarbons are not present means of a frit. Experimental and data analysis component for experiments with model oils. this speci:c point will be imum T -diJerence of ±2 K. From time to time it was side reactions can be neglected. (3) 2 mol H2 are The externally heated reactor had a length of 140 cm needed to convert 1 mol S (organic S) to H2 S. H2 -consumption Schmitz et al. New concept for deep desulfurization by a two-phase reactor with for the liquid is much lower than of a hydrogen recycle pre-saturator (the liquid recycle is an option not needed in case of deep compressor. a complete conversion of all S-compounds to Pre-saturator H2 S would only lead to a minor depletion (−7%) of the H2 dissolved H2 down to a value equivalent to a H2 -pressure of about 2:8 MPa (Fig. (2) adipic (for 100 % conversion by HDS) Limit of S-content of diesel oil acid-hexandiole-oligoester (Battsengel et al.5 1. Only in case of an oil with a still higher S-content and/or rich in unsaturates reactive for hydrogenation.) 4600 ppm S for the assumed pressure of 3 MPa. according to Henry’s law is established. So a H2 -consumption by nation with a level controller. an oil recycle would be needed (see Section 4. see text).. Schmitz. In all these cases.g. (5) With respect to kinetics veri:ed. 3 (oil + solid cat. even then a liq- Desulfurized oil uid recycle is more favourable than a gas recycle as needed for a trickle bed: The power consumption of a recycle pump Fig.0 0. 1997). respectively. Jess et al. to a typical case 1000 of a low concentration of the liquid reactant.e. C. 3. H2 : A sample of the oil (at reaction conditions) was taken actor.1 and 4.

pre-exponential fac- gaschromatograph clearly showed that no S-containing tors. thereby taking a of the relative low consumption ratio of 2 mol H2 per mol S.1.2824 C. The experiments were conducted with a commercial CoMo-catalyst (SIud-Chemie C20-6. At typical and 4. the S-content de. the temperature is given by k1 = k1.6-dimethyldibenzothiophene (4. aromatic ring(s). 2003).3). Model oils were ob. used in this work. The diesel oils with a S-content of 260 HDS-conditions (30 bar. The content of individual S-species like benzothiophene (BT). So most likely HDS on CoMo exclusively pro. the plot of log cS. Selected experiments were done with a smaller diam- eter of 0:2 mm by grinding the original catalyst. BET surface area: 245 m2 g−1 ). 4-MDBT and species other than the model S-compounds of the feed 4.. The inLuence of than 4-MDBT. was not detected (GC with Lame ionization detector). 4. This is con:rmed by an additional exper- tained by mixing n-dodecane with BT. again proves that the CoMo-catalyst used here is relative actor. Karlsruhe. k1 is the rate constant creases with increasing residence time. is justi:ed for the CoMo-catalyst as a feed. DBT. HDS of model oils (each) with individual sulfur compounds with a characteristic size of 1:7 mm (equivalent diameter of (CoMo-catalyst. (The values in brackets in cS = cS.) Model oils as well as two “real” pre-desulfurized biphenyl and H2 S without preliminary hydrogenation of the diesel oils were used as feedstocks. 0 are the residual and initial contents of the elementary analyser. 4 indicate slightly insecure results with S-contents less than 10 ppm. The calibration was adjusted for a range of 10–300 ppm S. area). It was beyond the scope of model oils) this study to explain this unexpected reaction order of zero with respect to H2 . activation energies) for HDS of DBT. able conversion of biphenyl—e. marizes typical results with model oils (semi-log plot). All experiments with individual S-compounds show that the HDS-reaction is :rst order with respect to the investi- 4. Above all. Ac- diJerences with respect to the reactivity of the investigated cording to Eq. dibenzothiophene (DBT). 4. This In addition to the experiments with the pre-saturation re. varied reaction temperature.6-DMDBT in n-dodecane) as used to compile Fig. HDS of individual S-compounds (experiments with 1 to 7 MPa (Schmitz. this may be ex- All HDS-experiments were conducted with the two-phase plained by the interplay of H2 -consumption and formation reactor (except those described in chapter 4. 2003). pyroLuorescence detector) with an error of about 1 ppm. of HDS-inhibiting H2 S (Vogelaar et al. So the decrease of the concentration of individual whereby each experiment was conducted with only one S-species is given by single S-species in n-dodecane. According to literature. i. The original catalyst has a special form of three interlinked cylinders Fig. 0 exp(−k1 ): (1) Fig. see text). this was not ceeds by the so-called direct route under formation of detected. (Although in case of the original catalyst “wall eJects” may contribute to a decrease of the achieavable conversion. (1). although with strong (m−3 kg−1 s1 ). should give a S-species. The analysis of the HDS product(s) by the S-sensitive The kinetic data (reaction order(s). out of the accurate range of calibration Thereby cS and cS. 0:31 g h cm−3 ).6-DMDBT (Table 2) were deduced from experiments with appeared. 360◦ C. at H2 -pressures from 1 to 7 MPa. tot vs. of the S-species (mgS =kgoil = ppm). / Chemical Engineering Science 59 (2004) 2821 – 2829 bed.g. 4-methyldibenzothiophene (4-DMDBT) and 4. to cyclohexylbenzene— Germany. 0 exp(−EA =RT). Results and discussion gated compounds. and residence times up to 1 g h cm−3 (ratio of mass of catalyst to feed rate of oil). 4. Schmitz et al. which is con:rmed by Fig.) As expected. comparative experiments were also conducted with inactive for hydrogenation of aromatics. 4-MDBT. tempera- tures of 340–400◦ C. feed: n-dodecane and in each case only one single S-compound. lines indicate :rst order reaction with respect to spheres with the same ratio of volume to external surface sulfur compound.6-DMDBT is much less reactive straight line. at least in the investigated range from 4. a measur- and 290 ppm were provided by MiRO re:nery. pressure and initial S-content . model diesel oil (300 ppm S as 4. Fig.6- DMDBT) was determined by a S-sensitive gaschromato- graph (GC Varian CP-3800 with pulsed Lame photometric detector (PFPD)). iment with biphenyl as feed (1% in dodecane). and the residence time (kg s m−3 ). 3. The total S-content was determined by elementary anal- ysis (Antek 9000. 3 MPa. 4 sum. So the assumption a trickle bed reactor (45 cm3 of catalyst). The inLuence of the H2 -pressure is neg- ligible (zero order).e. 360◦ C. DBT. and BT.6-DMDBT.

C. decreases with increasing degree of desulfurization by the tives can be well described by the kinetics obtained from increasing portion of the remaining. at least for the S-compounds investigated and the original particle size of 1:7 mm. The reliability of the kinetic data is given in Fig. dashed lines not determined because of its high reactivity. i.6-DMDBT 132 2:1 × 1011 2. CoMo-catalyst Measured S-content in ppm (C20-6. HDS of a model diesel oil consisting of a mixture of 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).g.6-DMDBT. Comparison of measured and calculated residual sulfur contents (details in Schmitz.e. and rate constant (360◦ C) for 360°C 380°C HDS of individual S-compounds (340–400◦ C. competing eJects in Table 2. with the rate constant k2 in m3 kg1 s−1 ppm1 . virtually lead. (1980) 1 1 10 100 1000 Calculated S-content in ppm Fig. 2003). 4). Sim. —e. original size of 1. It the rate of HDS (with respect to total S) superproportionally is interesting to note.7 and 0:2 mm).6-DMDBT. In case of BT. but this eJect can be 90 ppm S each) with n-dodecane) is shown in Fig. that the HDS of all three DBT deriva. 4-MDBT and DBT in n-dodecane (360◦ C. and so the intrinsic reaction rate was always measured.6-DMDBT in n-dodecane (300 ppm S). that no measurable aging of the catalyst occur within the investigated timeframe (500 h with diesel oil and 800 h with model oils). tion is about 20%. / Chemical Engineering Science 59 (2004) 2821 – 2829 2825 Table 2 1000 Activation energy. within the adjusted range of calibration of the elementary analysis (Antek 9000). Schmitz et al. tot. 6. It turned out that for the given conditions. kinetic data were (model oil with 4. 4). about 8 mm. .7 138 . (1) and the kinetic data (Table 2) are also indicated. pore diJusion would only have an eJect for a particle size (spheres) of more than Fig. (1) and the data given (total) S-contents of less than 300 ppm. cS. 4-MDBT and 4.6-DMDBT (about found for the individual S-species. 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. 2003). and that the reproducibility is very well. The aberra. 5 by the comparison of experimental and predicted values of the residual S-content based on Eq. tot = cS.6-DMDBT as example. 6) based on DMDBT. in case of the relative reactive DBT. tot. which strongly diJer in reactivity (see Fig. 6. The inLuence of pore or external diJusion on the ef- fective rate was excluded by variation of particle size (model compound DBT. S-content from 300 to 10 ppm. Reruns of experiments with model oil as well as with diesel oil indicate. by adsorption phenomena—can be neglected. less reactive compounds experiments with single S-species. 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. taking 4. i. 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. MDBT and comparison. So at least for initial like 4. 3 MPa). that e. 2003) indicate. 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. indicate 20% aberration). So Eq. For easily explained by the stepwise HDS of DBT. calculated results (lines in Fig.20 % a Houalla et al. Fur- ther calculations (Schmitz. 0 =[k2 cS. 1–7 MPa. 5. pre-exponential factor. ing to full conversion even for low temperatures and/or residence times (Fig. the rate is in- dependent of the particle size. 0 + 1] (2) ilar results were obtained for the other S-species (Schmitz.g.e.

7). see Schmitz. Germany). 8 the diesel oil (260 ppm S) and the calculation based on the shows characteristic S-species determined by chromatog. 390◦ C. (2) (1=cS. 360◦ C.) So at least in case of the two investigated diesel oils. As expected.6-DMDBT in diesel oil (as 4-MDBT or 4. 260 ppm S. 390◦ C. 2003. and mainly the multi-substituted S-compounds remain in inhibition of HDS by N-compounds (here about 90 ppm N the product oil. other conditions as given in Fig. 6 indicates that the re- Subsequent to the experiments with model S-compounds. (The raphy (PFPD-detector). above all in case of the diesel oil with two-phase reactor. only the refractory same result is obtained for the second diesel oil. S-sensitive chromatograms at diJerent stages of HDS of an already hydrotreated (pre-desulfurized) diesel oil (GC with PFPD. values calculated based on S-sensitive (PFPD) chromatograms). / Chemical Engineering Science 59 (2004) 2821 – 2829 60 4-MDBT in diesel oil 4. Deep HDS of diesel oil (feed: two already hydrotreated diesel oils Fig.8 Residence time τ in g. in Fig.6-DMDBT is not or only slightly lower in the diesel sent the plot of the linearized form of Eq. as shown by comparison of measured values in ) to con:rm the second-order reaction of HDS. 7 with Fig.2826 C. in both oils) and by aromatic hydrocarbons (not determined Fig. feed: diesel oil with 260 ppm S from MiRO re:nery in Karlsruhe. 4. straight (full) lines indicate of an already hydrotreated (pre-desulfurized) diesel oil (diesel oil with second order with respect to total S. Schmitz et al. . other conditions as given in Fig. 3 MPa. DBT-derivatives are present in the pre-desulfurized feed.6-DMDBT) 50 S-content in ppm 40 calculated curves for 1st 30 order reaction and the kinetic data given in Tab. The two straight lines repre. oil matrix. 7 with respect to the inLuence of the residence time the conversion rate of individual S-species like 4-MDBT on the total sulfur content. 9. 9). and 4. see Eq.6-DMDBT. 7. (2)).2.4 0. 7. Rest content of selected S-species at diJerent stages of HDS with 290 and 260 ppm Fig.2 20 10 0 0. action rate of HDS of both “real” diesel oil (with respect to two “real” pre-desulfurized diesel oils with 260 and total S) is lower than in case of a model oil even with the re- 290 ppm S were used as feedstocks for HDS in the fractory 4. Fig. respective kinetic data of HDS in n-dodecane (Fig.2 0. 8. tot vs.0 0. 7. HDS of pre-desulfurized diesel oil The comparison of Fig. Typical experimental results are shown an initial S-content of 290 ppm S (Fig.h. Nevertheless.6 0.

e. respectively. which are obvi. not possible.5 lower (Fig. sic rate reached with the two-phase reactor is in any case tion rate of the diesel oils (with respect to total S) is there. a noticeable de- to the respective experiment with the two-phase reactor. Nevertheless. 360◦ C. a higher reaction rate than the limiting intrin- —is irrelevant.2 (10 ppm S. e. 8).2 0. (3) The H2 -consumption is 2 mol H2 per mol S and 0:2 mm). Outlook: potential extension of the pre-saturation ethyl-groups (see Fig. no olefins) Residence time τ in g. scope of this study). is still relatively small.or 4. (2) For simpli:- diJusion have no inLuence on the eJective rate.6-DMDBT) 200 Trend 3-phase- reactor Two phase fixed- 150 Recycle pump bed reactor (recycle rate: 1. the pletion of dissolved hydrogen would occur in this case study reaction rate is by a factor of about 2. this limiting maximum rate is not above-mentioned minimum H2 -content at the reactor outlet reached. 2002. As already expected ac. e. of S-species. and 1 mol H2 per mol dodecene.h. but instructive case study in good agreement with the experimental :ndings with a to underline this suggestion.e. The two-phase reactor with pre-saturator is by far not the inLuence of the pressure is negligible.g. Compared gas–liquid mass transfer within the reactor. For the respective calcula- mixture of model S-compounds. probably because of improper gas–liquid distribu. The decrease of the tended to feedstocks rich in sulfur and/or unsaturated hy- total sulfur content with increasing residence time can be drocarbons.and C4 -DBTs with three or four additional carbon atoms as methyl. a liquid recycle is So only the two-phase reactor with pre-saturator utilizes the needed to compensate the lack of hydrogen. fore most probably the high content of C3 . So the main reason for the relative low reac. 7). So again.3. at least for the limited to the case of deep HDS. In case the recycle rate of less than two (1. all unsaturated hydrocarbons were considered as again proven by experiments with varied particle size (1. Koltai et al. technology ously even less reactive than 4. 11. comparative experiments were also conducted respect to kinetics. the following assumptions were made: (1) cording to the experiments with model oils (with equal or The pressure in the pre-saturator is 5 MPa.6-DMDBT) in n-dodecane.. 1997) Nevertheless. with respect to the velocity of the liquid and the gas phase.-% olefins) 2-phase-reactor 3-phase-reactor Pre-saturator 250 H2 S-content in ppm (as 4. by adjusting optimal conditions in this work)—as reported in literature (e. 20 wt.0 0. i. which is hydrocarbons for a simpli:ed. tion (Fig. thereby using a model oil In contrast to a trickle bed. SIud-Chemie CoMo-catalyst). with respect to the power consumption of a recycle reactor could possibly be improved (which was beyond the gas compressor compared to an oil pump. HDS in a conventional trickle bed reactor and in a reactor reactor with H2 -pre-saturation (assumptions see text). 1982. Comparison of deep HDS in the two-phase reactor all the ole:ns and to reach a residual S-content of 10 ppm. the intrinsic rates were measured. So the liquid-phase-only hydrotreat- tion and/or wetting of the catalyst.. where hydrogen is supplied by with 300 ppm S (as 4.68) needed to ensure the of the trickle bed reactor. which was cation. and can easily be ex- investigated range from 1 to 7 MPa. 0:7 mol H2 even higher intrinsic HDS reaction rates).8 1. Schmitz et al. 10. i. with a lab-scale trickle bed reactor.6 0. (4) The res- idence time is suTcient both for complete conversion of 4. Thereby must be empha. Ramachandran and Massoth. ing is certainly still more favourable than HDS in a trickle sized that probably the operation of the lab-scale trickle bed bed. .6-DMDBT in n-dodecane.4 0. 10).g. taking HDS of approximated quite well by assuming a second-order reac.0 1.4.68) (oil + solid cat. 11). 11. maximum (intrinsic) rate of the chemical reaction. a diesel oil with 5000 ppm S and 20 wt% of unsaturated tion with respect to total sulfur (lines in Fig.6-DMDBT. As in case of HDS of the investigated model S-compounds.) 100 50 Trend 2-phase- reactor Desulfurized oil 0 0. 3 MPa. Kabe et al. HDS of a diesel oil rich in sulfur and ole:ns in a two-phase Fig. This is illustrated by Fig. pore or external leave the pre-saturator per kg of oil. C. / Chemical Engineering Science 59 (2004) 2821 – 2829 2827 300 Oil (5000 ppm S. (with pre-saturator) and in a trickle bed reactor (5) A H2 -concentration at the reactor outlet equivalent to a partial pressure of H2 of 1 MPa is still suTcient with Finally. with H2 -pre-saturation of oil (model oil with 4. Fig.7 dodecene. within the two-phase reactor.

Deep desulfurization of fuels unsaturated hydrocarbons by installing a liquid recycle will by extraction with ionic liquids.g. The eJects of pyridine reactor is much easier than of a trickle bed reactor... B. 2002.... Sie. Development of deep hydrodesulfurization catalysts II.A.. Guevara. 2002. J.B. Jess... hydrogenation properties allow a rather easy hydrogenation of benzyl rings. Datsevich.und Makrokinetik mehrphasiger valid. (2) In contrast to HDS of diesel and fuel oil.. Jess. 239–254. Applied Catalysis A General 231. Einsatz eines Zweiphasenreaktors mit VorsIattiger fIur pre-saturation system has clearly one drawback in case of Mehrphasenreaktionen. Journal of Catalysis 61. von Veen. A. M.T. Neverthe- less. 2494–2495. Ph. Peter. mon hydrogen recycle needed for a trickle bed reactor. Mizuguchi. Schmitz et al. Q. C. 1980. 2003.. Datsevitch. pre-saturation technology to feedstocks rich in sulfur and/or Esser. L. Pt and Pd catalysts tested with (substituted) dibenzothiophene.. If a liquid recycle is needed for a Wasserscheid. Jess. D. N.. D.. new technology utilizes the maximum (intrinsic) chemical Navarro..R. Schulz. C. Catalysts for second-stage deep installed. S. A. which is still much less expensive than the com.... In this case.. Deep hydrodesulfurization of DBT this rate is an upper limit. Vasudevan.. which can not or only hardly be and diesel fuel on supported Pt and Ir catalysts. Model oils Engineering & Technology 25. a liquid recycle has to be Veen. and a Granada. Kinetic behaviour of hydrogenation of aromatics in diesel fuel over silica-aluminia-supported bimetallic Pt–Pd catalyst.T. van sulfur and/or ole:ns. 253–261. Pawelec. Luid catalytic cracking). S. New York. are used in the second step of HDS.R. the extension of the organic compounds. 226th American Chemical Society have to be further investigated by respective experiments in (ACS) National Meeting. Vrinat. HDS of gasoline rich in ole:nes and/or aromatics (e. 1. 1–7 MPa. hydrodesulfurisation of gas oil. Forissier. BP Oil. van Langveld... Kabe. and then much more hydrogen than just 2 References mol per mol of organic sulfur will be consumed.. option for HDS of diesel oils (and other gas oils) rich in Reinhoudt. Fierro. S. Thesis. E.. Pitault. Moulijn... 2003. Otsuki. Battsengel. a classical trickle bed reactor with the new two-phase tech. Kinetics ized and therefore hydrogenated diesel oils were used as and mechanisms of dibenzothiophene hydrodesulfurization. K. J. Aachen.. M. is by far enough for HDS of already hydrotreated oil.. 547–553. P.R. University of of oil would be needed as outlined before. 553–558. Lauter.J. Sapre. Applied Catalysis A General 205. 1996.F.or Pt-Pd-based systems spe.L. Ni. H. rate of the HDS reaction.. Panten.R. L.. Wasserscheid.... lined theoretical considerations. Arias. MIunnich.. Bacaud. A. (4) Fur... SUDCHEMIE for supplying the catalyst. K... 5146–5152. R. schaft (Je 257/2) and BP Oil is gratefully acknowledged. Conclusions Houalla. oil using a two-phase reactor (pre-saturated oil and solid cat.. CoMo-catalyst). W. Experimental and theoretical alyst) was investigated under typical reaction conditions of studies on hydrogenation in multiphase :xed bed reactors. Zur Kinetik und zur verbesserten ReaktionsfIuhrung We thank Nick J. A. T. Ishihara..A.2828 C. On the basis of the experiments and of the out. A. Mukhortov. the liquid-phase-only HDS is also an interesting Communication 18. 1999. Deep hydrodesulfurization of light gas oil.. Hydrodesulfurization of methyl-substituted dibenzothiophenes catalyzed by sul:ded Co–Mo= A new concept for hydrodesulfurization (HDS) of diesel –Al2 O3 . J. Ph. 269–286. K.. Deep desulfurization of diesel fuel suTcient H2 -supply.. 523–527. L.. D. Lemaire. the basic principle of the pre-saturation concept is still Battsengel. M.. Thesis. Peter.L.A. A. 5. Kwart. Moulijn..... Nag.D. de Beer. but a higher total pressure and/or higher recycle rate heterogen-katalysierter Reaktionssysteme. B.. A. Turek.D. H.. which is not favorable. NiW. So Schatkowski. F. B.. C..M... D. Applied Catalysis A reached. Schmitz. Zhang. 21–25 September 2003. H2 -recycle is obsolete.. Sunbury-on-Thames.. W.g.. solubility in straight run gasoil.V. Chemical Engineering Science 57. (1) If other catalysts. Gudde (Re8ning Technology. (2) The amount of H2 dissolved in the pre-saturator General 137. T... Patent RU 2083540. Zur Mikro. Engineering Chemistry Research 36.G.. the octane number of the product is by extraction with ionic liquids. Usui. V.. J.. Chemie Ingenieur Technik 75. Fuel Processing Technology 61.. P.. their oil samples. P. K. Massoth. 7–11.. de Beer. P. A. 2003. J. from BIosmann. presumably decreased.J.. Ronze. Fongarland. Comparative inhibiting eJect of polycondensed nology clearly shows the advantages of the latter: (1) The aromatics and nitrogen compounds on the hydrodesulfurization of alkyldibenzothiophenes. Industrial feedstocks. W. Godo. e. Robinson. Jess.A.. R.A. 271–277. T. Broderick. Fuel Acknowledgements Processing Technology 61.. . R.H.. I. Troost. Cambra. 2002... J.A. L. Akamatsu. / Chemical Engineering Science 59 (2004) 2821 – 2829 Two aspects should :nally be mentioned:  and comments. H. Qian. A. A.H. 133–147. Spain. and coke poisoning on benzothiophene hydrodesulfurization over cobalt-molybdenum/alumina catalyst. T. 2001. Fujikawa. Chemical Communications 23. M. 1997. Datsevich. Jess. J. and the MiRO re:nery (Karlsruhe) for supplying the diesel ci:c for deep HDS. Technology. Chemical engineering aspects of hydrogenation there is no need of the presence of gaseous H2 within the of :ne chemicals. reactor to supply additional H2 into the liquid phase. with dibenzothiophene derivatives as well as predesulfur. Idei. M.E. order to prove the theoretical suggestions outlined above. 103–116. V. P. J.. (3) The scale-up of the two-phase Ramachandran. M. Great Britain) for fruitful discussions University of Bayreuth. whereas in case of a trickle bed Guemez. R. 621–626. 2003. Chemical Engineering thermore. Datsevich. the Battsengel.K. Chemical HDS (340–400◦ C. Gates.. 1999.. S.D. 1997.. Schmitz. Hydrogen Financial support by the Deutsche Forschungsgemein. M. Macaud. Process for hydrogenation of So in future experimental work. Fourth European Congress of Chemical Engineering. B. the comparison of HDS in Koltai. 2002. 1982.. 2001. September 2003. Datsevich.. Pickenhagen. B. der hydrierenden Tiefentschwefelung von DieselIol. A. L.H. Ohki.C.

A. pressure. 226th American Chemical Society (ACS) National Meeting. 2003.. 359–364. S.. .L. 226th catalyzed by various Co–Mo=Al2 O3 and Ni–Mo=Al2 O3 catalysts. (part 4). Gudde. B. C. Kabe. Chemistry added design of future clean fuels. C... 2003. Datsevich. N. N. Hydrodesulfurization of methyl-substituted dibenzothiophenes Sughrue. / Chemical Engineering Science 59 (2004) 2821 – 2829 2829 Schmitz.. Ishihara.A. E. Active sites and activity: the eJect of H2 and H2 S partial and a recycle. American Chemical Society (ACS) National Meeting. Kagami. A. 7–11 September 2003. Deep desulfurization of light oil reactors. Eijsbours..M.. 1996. New York. New York.. Schmitz et al. Journal Japanese Petroleum Institute 39. 7–11 September 2003.D. Improvement of Vogelaar. Jess. Process intensi:cation in in-line monolithic Zhang. A. Q. T. Stankiewicz. 2003. Spain. 410–417. the deep desulfurization of fuels by the employment of a pre-saturation J. Moulijn.. Granada. Chemical Engineering Science 56. von Langeveld. A..J.. 2001.. 21–25 September 2003... 4th European Congress of Chemical Engineering. L.