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Journal of Colloid and Interface Science 372 (2012) 121129

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Journal of Colloid and Interface Science


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A comparative kinetic study on ultra-deep hydrodesulfurization of pre-treated gas oil over nanosized MoS2, CoMo-sulde, and commercial CoMo/Al2O3 catalysts
Hamdy Farag a,b,, Isao Mochida c
a

Department of Material Process Engineering, Graduate School of Engineering, Kyushu University, Motooka 744, Fukuoka 819-0395, Japan Chemistry Department, Faculty of Science, Mansoura University, 35516, Egypt c Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka 816-8580, Japan
b

a r t i c l e

i n f o

a b s t r a c t
Unsupported nanosized MoS2 and CoMo-sulde catalysts were synthesized, and their catalytic performances for the deep hydrodesulfurization (HDS) of treated gas oil were investigated as compared with that of a CoMo/Al2O3 catalyst. The HDS reactions were carried out in a batch autoclave reactor at 340 C and 3 MPa H2. The CoMo-sulde catalyst shows the highest activity and can reduce the sulfur content to less than 10 ppm. The decrease in total sulfur content as a function of reaction time was found to follow pseudo-second order kinetics (empirical form). The change in the concentration of some individual representative sulfur-containing species in gas oil as a function of time was found to follow pseudo-rstorder kinetics. However, the change in combined concentration of these species in the gas oil during HDS with the reaction time was found to corroborate pseudo-second-order kinetics. A kinetic model approach was proposed from which an estimation of the intrinsic kinetic data can be achieved. The model tted the obtained data reasonably well, suggesting its potential for better assessment of the catalytic activity in the HDS of real feedstock. The study reveals that ranking of catalyst activities using model refractory sulfur-containing compounds does not necessarily imply a typical rank in case of investigating the real feedstocks. 2012 Elsevier Inc. All rights reserved.

Article history: Received 16 November 2011 Accepted 9 January 2012 Available online 18 January 2012 Keywords: Hydrodesulfurization Gas oil MoS2 Catalyst

1. Introduction Catalytic hydrodesulfurization (HDS) is recognized as being the most effective and reliable process for reducing the sulfur content in gas oil to meet stringent regulations recently adopted all over the world; a sulfur limit of 15 ppm or less has been already adopted by the developed countries [15]. For a typical gas oil, this sulfur content corresponds to a signicant high conversion level of all the sulfur-containing compounds. Sulfur-free diesel has been proposed as a future specication for use in a number of applications [6]. For instance, use in fuel cell applications is increasingly promising as the existence of sulfur-containing compounds, even in low amounts, can have a severe poisoning effect on noble catalysts. The poisoning effect on catalysts is such that a catalyst effective for fuel cell reactions may easily become ineffective or short-lived in the presence of even traces of such species [6]. The key factor in the HDS process is the identity of the catalyst where a high activity is mandatory. Reneries most often use CoMo- and
Corresponding author at: Department of Material Process Engineering, Graduate School of Engineering, Kyushu University, Motooka 744, Fukuoka 819-0395, Japan. Fax: +81 92 802 2792. E-mail addresses: hamdy@chem-eng.kyushu-u.ac.jp, hamdy.farag@gmail.com (H. Farag).
0021-9797/$ - see front matter 2012 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2012.01.019

NiMo-based catalysts [1,2]. However, recently, a series of alternative catalyst candidates relying on unsupported metal sulde phases have been proposed for use in the hydrotreatment of renery streams [711]. One such group of catalysts, termed bulk catalysts, is formed from the transition metal sulde alone or is mixed with other metal compounds, usually by co-precipitation techniques, where there is no catalyst carrier or support [8]. For instance, nanosized MoS2 catalysts have been found to show promise activity in the HDS of model refractory sulfur-containing components [10,12,13]. It would be of interest to investigate further the behavior of such catalysts with real feedstocks such as gas oil. Gas oil consists of a mixture of hundreds of parafns, naphthenes, aromatics, polyaromatic sulfur-containing compounds, and polyaromatic nitrogen-containing compounds. The catalyst activity in HDS is seriously affected by a variety of contaminants contained in feedstocks [1420]. The existence of H2S and nitrogen-containing compounds, for instance, showed dramatically detrimental effects on catalyst activity. However, the extent of response of one catalyst to such species depends on the catalyst identity [12,13]. The HDS reaction rate is markedly affected by the existence of even trace amounts from such species. Polyaromatic sulfur-containing compounds are well known to be the most refractory sulfur-containing compounds in middle distillates [1,2]. For effective HDS activity, and especially for achieving ultra-low sulfur fuel to meet

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the recent environmental regulations, a catalyst must be effective in removing all refractory sulfur-containing compounds [21]. The process is, in fact, still in need of further investigation to fully understand the chemistry associated with removing these refractory species. The HDS of such species proceeds through two parallel reaction pathways: (1) the direct hydrogenolysis of the CS bonds and (2) the hydrogenation of one of the benzene rings prior to rapid hydrogenolysis. A catalyst of heightened selectivity toward one of these catalytic routes for the HDS of polyaromatic sulfur-containing compounds is important for ultra-deep HDS. Little information is available in literature regarding the HDS of real feedstocks (e.g., gas oil) over unsupported nanosized bulk metal sulde catalysts in comparison with the conventional CoMo- and NiMo-based catalysts [2229]. The results may be of interest as the data obtained from gas oil and model sulfur compounds are not always straightforward. The HDS of model refractory sulfurcontaining compounds (dibenzothiophene and 4,6-dimethyldibenzothiophene) over nanosized MoS2 proceeds mainly via a signicant contribution from the hydrogenation route [10 13]. On the other hand, the conventional catalysts, that is, CoMoand NiMo-based catalysts, perform the reaction via a considerable contribution from both these routes. As such species and their derivatives are the most refractory sulfur-containing compounds in HDS, it would be worthwhile investigating their reaction performance in real feedstocks. Studies have shown that the activity for the hydrogenation pathway is much more important than the direct desulfurization pathway (DDS) in the HDS of these components [7,8,13]. In this study, a feedstock of gas oil was investigated for HDS over synthesized unsupported nanosized MoS2, CoMo-sulde, and commercial CoMo/Al2O3 catalysts. To alleviate or avoid inhibition by nitrogen species, pre-hydrotreated gas oil was used. The catalytic properties of the synthesized nanosized MoS2, CoMo-sulde, and commercial CoMo/Al2O3 catalysts in deep HDS of this gas oil under renery operating conditions were compared. The kinetics of the HDS was also studied.

2.2. Catalysts Three catalysts, synthesized nanosized MoS2 (MS), synthesized CoMo-sulde (CMS), and commercial CoMo/Al2O3 catalysts, were implemented in this study. The nanosized MoS2 catalyst was synthesized according to the method described in detail elsewhere [10]. Briey, ammonium heptamolybdate tetrahydrate was the starting molybdenum precursor. The molybdenum precursor was heated under the continuous ow of an Ar atmosphere to 300 C. Then, the inlet gas was converted to H2S/H2 (10% (v/v)), with a ow rate of 60 SCCM. The temperature was raised to 830 C at 2 C/min. The sample was maintained at 830 C and a ow of H2S/H2 of 10% (v/v) for 3 h. Thereafter, the reactor was ushed using Ar for approximately half an hour. The obtained sample was kept in a desiccator for further investigation. The sample was milled using an agitating-media mill with inner volume of 80 ml for 24 h using zirconia beads of a diameter of 3 mm. The CMS catalyst was synthesized where MoS2 was used as a preliminary support for the cobalt phase. The unsupported CoMo sulde catalysts with Co/ (Co + Mo) atomic ratio of ca. 0.05 were synthesized as follows. Firstly, thermal treatment of ammonium tetrathiomolybdate (NH4)2MoS4 was carried out under a continuous ow of 10% v/v H2S/H2 gas mixture at 420 C. This step yields the MoS2 phase. Then, 0.5 g of cobalt nitrate hexahydrate (Co(NO3)26H2O) was dissolved in distilled water, to which 20 mL of 1 M ammonia solution was added. The ammonical cobalt solution was poured into a slurry solution containing 3.2 g of the previously synthesized MoS2. The slurry was then subjected to ultrasonic vibration for 1 h, stirred in air over a water bath at 45 C for approximately 6 h to gently evaporate the solvent, and then dried in a vacuum oven overnight at 120 C. The precursor was sulded again under a 10% v/v H2S/H2 gas mixture at 400 C; thereafter, the sulding gas was purged for 30 min using Ar. Specications of the catalysts are summarized in Table 2. Immediately before carrying out the catalytic tests in the HDS, each catalyst was subjected once more to suldation using the H2S/H2 gas mixture. The BET-surface areas were measured using an automatic sorptomatic apparatus (Quantachrome) at liquid nitrogen temperature. Activation treatments were carried out at 300 C. X-ray diffraction studies were carried out in a Rigaku Diffractometer using Cu Ka radiation (k = 1.54056 ) and operating at 43 kV and 30 mA. Transmission electron microscopy (TEM) was used for lattice imaging and electron diffraction of nanoparticles. Imaging were obtained in a Hitachi 9000UHR working at an accelerating voltage of 200 kV.

2. Experimental section 2.1. Materials Pre-hydrotreated gas oil was provided from the Japan renery. The initial sulfur content of this gas oil was 360 ppm S with additional specications listed in Table 1. All chemicals in this study were purchased from the Wako Chemical Co. and were used without any further purication.

2.3. Catalytic activity Catalyst performances were investigated for the HDS of gas oil. The reactions were carried out in a high pressure batch system using a magnetically stirred microautoclave reactor (100 ml

Table 1 Specication of gas oil. Density (g/cm3, @15 C) S content (w/w-ppm) Nitrogen (w/w-ppm) Chemical composition (vol%) Parafn Olen Mono-aromatics Di-aromatics Tri-aromatics Boiling points (C) 10 vol% 50 vol% 90 vol% Cetane index 0.835 360 3 78.3 0 19.3 2.4 0 249.5 297 357.5 61.8

Table 2 Specications of catalysts. CoMo/Al2O3 Metal (%, in the oxide form as received) Co Mo Surface area (m2/g, BET-N2) Pore volume (ml/g) MS Surface area (m2/g, BET-N2) Pore volume (ml/g) CMS Surface area (m2/g, BET-N2) Pore volume (ml/g)

3 12.4 210 0.4 100 0.5 47 0.3

Measurements were conducted by renery provided this oil.

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capacity). This reactor was designed to allow for the withdrawal of sample at time intervals during the reaction. In all runs, the catalysts were investigated at typical reaction conditions. Prior to the reaction, the catalyst was sulded at 400 C for 3 h, by a stream of 10 v/v% H2S/H2 with a ow rate of 60 SCCM. In a typical experiment, 15 ml of gas oil was loaded into the reactor with 0.020.1 g freshly sulded catalyst (nanosized MS, CMS, and/or CoMo/Al2O3 catalysts). The stirrer speed was adjusted to 1000 rpm, and the reactor purged several times with H2 before the reaction pressure was set at 3 MPa H2. All the HDS reactions were nally carried out at 340 C. During the reaction, small aliquots of less than 0.1 mL were withdrawn at various time intervals for analysis. Total sulfur content in the hydrotreated gas oil during the reaction was determined using a gas chromatograph (GC) equipped with sulfur chemiluminescence detector (CLD) and methylsiloxane capillary column (0.32 mm 50 m, HP6890) with the aid of a standard gas oil sample. Identication of some sulfur species in the hydrotreated gas oil was achieved using standard sulfur-containing compounds. The quantity of some individual sulfur-containing species was estimated from standard calibrations of analogous known samples in terms of the GC-CLD chromatogram area. The conversion of total sulfur was calculated as follows:

300

CMS
200

100

Intensity, CPS

0 300

MS
200

100

HDS %

SI SF SI

100

20

40

60

80

100

where SI and SF are the concentration of total sulfur in ppm (weight) in the feedstock, before and after the HDS reaction, respectively. 3. Results 3.1. Catalyst characterizations Fig. 1 reports the XRD patterns obtained for the synthesized MS and CMS catalysts. Broad peaks at 2h = 14, 34, and 59 characterized for MoS2 hexagonal structure were observed. The patterns illustrate typical scans that are characteristic of poorly crystalline MoS2 structure. They are similar to those reported in JCPDS data for crystalline MoS2-2H (PDF: 6-97I). The XRD peaks indicate a very poorly crystalline structure of MoS2 characterized by a low stacking of layers along the c direction. Inclusion of Co-phase into MoS2 did not make any important change in the XRD pattern of MoS2. The lack of obtaining any peak assigned for Co-phase can be attributed to the low loading amount of Co-phase. The average crystallite sizes of MS and CMS catalysts estimated from the XRD patterns in the (0 0 2) plane were 4 and 3.8 nm, respectively. The BET surface areas for MS and CMS catalysts were estimated to be 100 and 47 m2/g, respectively. Surface characteristics of catalysts are reported in Table 2. TEM micrographs are reported in Fig. 2a and b, for MS and CMS catalysts, respectively. These images show the well-known characteristic fringes of the layered MoS2-phases. The number of stacked layers generally varies between 3 and 7. 3.2. Hydrodesulfurization of gas oil The pre-hydrotreatment of the gas oil affects the nitrogen level signicantly. The HDS of the sulfur-containing compounds in this gas oil proceeds with minimal inhibition owing to the nitrogencontaining species [16,18]. This gas oil contains a complex mixture of sulfur-containing components of more than 60 different species. Fig. 3 shows the HDS reaction data represented by the change in sulfur content of pre-hydrotreated gas oil as a function of reaction time for nanosized MS, CMS, and CoMo/Al2O3 catalysts. It is interesting to note that both the nanosized MS and CMS catalysts exhibit higher activity than the commercial CoMo/Al2O3 catalyst. The data obtained over all catalysts are well matched with second or-

2
Fig. 1. Powder XRD pattern of synthesized MS and CMS catalysts after suldation with 10 v/v% H2S/H2 gas at 400 C.

Fig. 2. Transmission electron microscopy (TEM) micrographs of the MS (a) and CMS (b) catalysts after suldation with 10 v/v% H2S/H2 gas at 400 C.

der kinetics in respect to the total sulfur content. The pseudo-second-order plots of the conversion of sulfur compounds in the pretreated gas oil over the present catalysts are shown in Fig. 4. It

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350 280

CMS MS CoMo/Al2O3

210 140 70 0 0 200 400 600 800

Time, min
Fig. 3. HDS kinetics of gas oil (decrease in total sulfur content with time) over MS, CMS, and CoMo/Al2O3 catalysts.

agreement with those reported for such reactants when used singly. Alkyl-substituted dibenzothiophenes were selected for investigation because of their low reactivity in the HDS reaction. The reactivity of these species toward HDS over the present catalysts can be ranked as follows: DBT > 4-MDBT > 4,6-DMDBT. Results in Tables 1 and 2 demonstrate that the CMS catalyst is the most active catalyst for the HDS of gas oil in comparison with the other catalysts. Table 4 shows the total sulfur content as well as the sulfur content in a form of some identied sulfur species in the gas oil after the HDS reaction over the present catalysts. The data show that the catalyst activities are ranked in decreasing order as follows: CMS > MS > CoMo/Al2O3 catalysts. One may notice that the sulfur content in the form of alkyl-substituted dibenzothiophene makes up a signicant ratio of the total sulfur contained in this gas oil. This highlights the importance of nding a catalyst of potential activity to transform such species for achieving an ultra-low sulfur fuel.

Total S in ppm

must be noted that this second order t is simply an empirical presentation of data and provides no description of the reaction mechanism. For comparison, the activity was normalized per unit surface area, per unit metal content, as well as per unit volume of catalyst. The normalization based on unit volume was calculated using an experimental packing density of 1.35, 1.40, and 0.70 g/ cm3 for MS, CMS, and the commercial CoMo/Al2O3 catalysts, respectively. The estimated data are presented in Table 3. The rate constant, estimated with respect to surface area, for the nanosized MS catalyst in the HDS of pre-treated gas oil is ca. 10 times larger than that for CoMo/Al2O3. Furthermore, the CMS shows an order of magnitude higher activity than that of the CoMo/Al2O3 catalyst. Furthermore, the activity of CMS catalyst normalized to total metal concentration is ca. 4 times larger than that of CoMo/Al2O3. This trend in activity may also be observed for the reaction of some selected singly investigated sulfur-containing species. This means the nanosized MS and/or CMS may have more potentially active sites per unit surface area than the CoMo/Al2O3 catalyst. The conversion of selected sulfur-containing compounds in gas oil, that is, dibenzothiophene (DBT), 4-methyl-dibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), can be well approximated by applying pseudo-rst-order kinetics as presented in Figs. 5a, 6a, and 7a for the HDS reaction over MS, CMS, and CoMo/Al2O3 catalysts, respectively. These results are in

4. Discussion 4.1. Kinetics of hydrodesulfurization of some model sulfur-containing compounds in gas oil Although the kinetics of the HDS of some model sulfur compounds have been reported widely in literature [1,15,2836], studies on the HDS kinetics of real feedstocks are relatively limited. This is probably owing to the presence of a large variety of sulfur compounds with different reactivities [27,36]. The refractory sulfur-containing compounds accumulate in the high boiling feedstocks making up a signicant ratio of the total sulfur content. Thus, to achieve ultra-deep-HDS, it is necessary to remove such species effectively. It is important to evaluate the kinetic behavior of such species inside the real feedstock. A better insight into the potential difference between the present catalysts in the HDS of the pre-treated gas oil can be gained by investigating the kinetic behavior of some representative individual sulfur compounds in this feed. Figs. 5a, 6a, and 7a show pseudo-rst-order plots of the HDS of DBT, 4-MDBT and 4,6-DMDBT in gas oil over MS, CMS, and CoMo/Al2O3 catalysts, respectively. Pseudo-rst order kinetics represents satisfactorily the experimental data with regression factors in the range 9699%. These results are generally in agreement with those reported in literature for similar model species [4,22]. The estimated kinetic data are described in Table 5. One may see that 4,6-DMDBT is the most refractory sulfur-containing compound toward HDS. The rate of disappearance of DBTs over all examined catalysts decreased in the following order DBT ) 4MDBT > 4,6-DMDBT, indicating that alkyl groups next to the sulfur atom hinder the HDS reactions, and the degree of inhibition increases as the number of alkyl groups around this sulfur increases in agreement with other studies in the literature [5,15]. According to the estimated pseudo-rst order rate constant, 4,6-DMDBT is ca. 2.4, 1.7, and 2.3 times less reactive than DBT in the HDS over CMS, MS, and CoMo/Al2O3 catalysts, respectively. This is well known to be attributed to the steric hindrance exerted by the substituted methyl groups in the 4- and 6-positions, which limits the approach of the compounds to the catalytic active sites. The reactivity of the DBT components over the CoMo/Al2O3 and metal-sulde catalysts suggests that the HDS of these sulfur species proceeds by means of a typical mechanism over these catalysts. A similar behavior was observed for the HDS of model DBT components over analogous catalysts [3033,37] The reactivity trend for the HDS of the representative refractory sulfur-containing components over all the present catalysts was the same. It is clear that the nanosized metal-sulde catalysts are signicantly more active for the HDS of the refractory sulfur-containing compounds than the CoMo/Al2O3

0.14 0.12 CMS MS

1/S content, ppm

0.1 0.08 0.06 0.04 0.02 0 1

CoMo/Al2O3

10

100

1000

Time, min (log scale)


Fig. 4. Pseudo-second-order plots of the HDS of gas oil over MS, CMS, and CoMo/ Al2O3 catalysts at 340 C under 3 MPa H2.

H. Farag, I. Mochida / Journal of Colloid and Interface Science 372 (2012) 121129 Table 3 Pseudo-second order rate constants and half-life of the sulfur content in gas oil hydrodesulfurization over nanosized metal suldes and CoMo/Al2O3 catalysts. Catalyst Apparent rate constants, half-life and relative activity at different consideration ka CoMo/Al2O3 MS CMS 1 10 3 104 20 104
4

125

t1/2a 28 9 1

RAd 1 3 20

kb 1 10 2 104 14 104
4

t1/2b 20 13 2

RA 1 2 14

kc 5 10 50 107 425 107


7

t1/2c 5555 555 65

RA 1 10 85

ke 9 104 5 104 33 104

RA 1 0.5 4

Factor of error: 27%. a Apparent rate constant, ppm(wt)1 min1 gcat1, normalized per unit weight of catalyst and the corresponding half lifetime, minute. b Apparent rate constant, ppm(wt)1 min1 mL cat1, normalized per unit volume of catalyst and the corresponding half-life, minute. c Apparent rate constant, ppm(wt)1 min1, normalized per unit surface area of catalyst and the corresponding half-life, minute. d Relative activity calculated as the ratio of k of the nanosized MoS2 catalysts to that of the CoMo/Al2O3 catalyst. e Apparent rate constant, ppm(wt)1 min1, normalized per unit of total metal (Co + Mo) concentration and the corresponding half-life, minute.

(a)

(b)
1/S content

0.06

0.04

Ln (S in ppm)

0.02

0 1

100

200

300

Time, min
0 Experimental Fitted

100

200

300

Time, min
DBT Fitted 4-MDBT Fitted 4,6-DMDBT Fitted

Fig. 5. Pseudo-rst-order kinetics of DBT, 4-MDBT, and 4,6-DMDBT (a) and second order plot of combined content of DBT, 4-MDBT, and 4,6-DMDBT (b) in gas oil HDS over MS catalyst at 340 C and 3 MPa H2.

(a)

(b)
1/S content

0.2

0.1

Ln (S in ppm)

1 0 0 0 100 200 300 400

Time, min
Experimental Fitted

100 DBT Fitted 4-MDBT

200

300 Fitted

400

Time, min
4,6-DMDBT Fitted

Fig. 6. Pseudo-rst-order kinetics of DBT, 4-MDBT, and 4,6-DMDBT (a) and second order plot of combined content of DBT, 4-MDBT, and 4,6-DMDBT (b) in gas oil HDS over CMS catalyst at 340 C and 3 MPa H2.

catalyst. The superior activity of metal-sulde catalysts over the CoMo/Al2O3 catalyst can be attributed to their higher hydrogenation activity, which is considered essential for the HDS of such alkyl DBTs [10,12,15] and their high tolerance for the HDS reaction inhibitors [38,39].

4.2. Kinetics of combined hydrodesulfurization reaction of DBT, 4-MDBT and 4,6-DMDBT Various studies have been devoted to exploring the aggregated kinetic behaviors of sulfur-containing components in real

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(a)

(b)
1/S content

0.04

0.03

Ln (S in ppm)

0.02

0.01 0

100

200

300

Time, min
Experimental Fitted

100 DBT Fitted 4-MDBT

200

300

Time, min
Fitted 4,6-DMDBT Fitted

Fig. 7. Pseudo-rst-order kinetics of DBT, 4-MDBT, and 4,6-DMDBT (a) and second order plot of combined content of DBT, 4-MDBT, and 4,6-DMDBT (b) in gas oil HDS over CoMo/Al2O3 catalyst at 340 C and 3 MPa H2.

Table 4 Distribution of some refractory sulfur-containing compounds in gas oil before and after the HDS reaction over nanosized metal suldes and commercial CoMo/Al2O3 catalysts. Sulfur species S (ppm) S (%) Catalyst CoM/Al2O3 (242 min) S (ppm) Total S in gas oil DBT 4-MDBT 4,6-DMDBT 360a 5.1 19.1 67.8 100.0 1.4 5.3 18.8 207 0 5.8 21 %Conv. 42.5 100.0 69.6 69.0 MS (205 min) S (ppm) 115 1.1 5.4 14.1 %Conv. 68.1 78.4 71.7 79.3 CMS (260) S (ppm) 23 0 1.2 5 %Conv. 94 100 95 93

Reaction conditions: 340 C and 3 MPa H2; 0.1 g catalyst was used in all tests. a Total sulfur content in the gas oil before the HDS reaction.

Table 5 Pseudo-rst-order rate constants of some refractory sulfur-containing compounds in the HDS of gas oil over nanosized MS, CMS and commercial CoMo/Al2O3 catalysts. Sulfur component Catalyst CMS Rate constants k (s1 g cat1 104) DBT 4-MDBT 4,6-DMDBT 18.8 13.5 7.8 First Order half-life DBT 4-MDBT 4,6-DMDBT 6.1 8.6 14.8 9.9 11.0 16.3 10.5 15.2 24.6 11.7 10.5 7.1 11.0 7.8 4.7 MS CoMo/Al2O3

Combined rate constants (s1 g cat1) (1st); (ppm1 s1 g cat1) (2nd) k2nda k1stb (t1/2)1stc (t1/2)2ndc 8.3 105 40.1 104 8.6 6.7 2.6 105 29.3 104 11.7 10.8 1.3 105 23.5 104 15.0 16.0

Factor of error: 27%. NB: Initial experimental points were not considered on estimating the kinetic parameters. a Pseudo-second-order rate constant for combined DBT, 4-MDBT, and 4,6-DMDBT. b Pseudo-rst-order rate constant for combined DBT, 4-MDBT, and 4,6-DMDBT. c Half-life of second order and average half-life of rst order in minute for conversion of the sulfur species.

feedstock [34,35,40]. The HDS of gas oil is often treated by a combined kinetic model because of the existence of a rather high number of various sulfur-containing components. Therefore, a wide range of reactivities is expected for these components. While the HDS reactions of individual sulfur-containing compounds exhibit

mostly rst order kinetics, the overall reaction of the mixture in real feedstock often shows higher order kinetics [34,35]. In the present study, the change in concentration of some refractory sulfur-containing components (i.e., DBT, 4-MDBT, and 4,6-DMDBT) contained in gas oil as a function of time was found to t pseu-

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do-rst order kinetics reasonably well. Thus, there is a need to solve these peculiarities in light of detailed kinetic analysis. As most model sulfur-containing compounds have proven to follow pseudo-rst order kinetics in the HDS reaction, it may be more interesting to evaluate the kinetic behavior of these species when they exist together in real feedstock under the same reaction conditions. It has already been mentioned that the overall reaction of total sulfur removal follows pseudo-second order kinetics (Fig. 2). The half-life of a compound is highly dependent on the order it follows. For a rst order reaction, the half-life is independent of the initial concentration. Physically, this means that whatever the initial concentration is, a half of its content will be transformed via the reaction in a typical time; that is, the concentration drops by a factor of two for every t1/2 increment in time. Unlike the rst order reaction, the second order half-life is inversely proportional to the initial concentration of the component. The kinetics of the combined concentrations of DBT, 4-MDBT and 4,6-DMDBT follow a second order equation as described in Figs. 5a, 6a, and 7a. However, this second order has no implication, in terms of kinetics, on the mechanism of the HDS of the components. Some interesting points can be estimated and extracted from investigating the behavior of the combination of these sulfur-containing components based on rst-order kinetics. Table 5 shows the data estimated from a second-order representation of combined DBT, 4-MDBT, and 4-MDBT in comparison with their individual rstorder manipulation. A model approach to treat these data kinetically is described below. 4.3. Mathematical approach For rst-order reactions, the following equations were applied:

DMDBT was also proven to t the second-order kinetic equation and can be described as follows:

  1 1 P P k2nd t C Ai C Ai
This may lead to the following approximation:

    C A1 C A2 C Ai k1st 1 1 % Ln P P C Ai C Ai C A1 C A2 C Ai k2nd

Eq. (9) is a linear equation that can be easily solved to estimate the ratio of k1st/k2nd. All these functions were solved to t the obtained experimental data using the least square regression method with the aid of Mathcad software. 4.4. Catalyst performances Figs. 5a, 6a and 7a show the pseudo-rst order plots of change of DBT, 4-MDBT, and 4,6-DMDBT concentration in gas oil as a function of time. The change in combined concentration of DBT, P 4-MDBT, and 4,6-DMDBT in the form of 1/ CAi during the HDS reaction as a function of time was found to corroborate secondorder behavior (Figs. 5b, 6b and 7b). The slope of this linear line is the empirical second order rate constant where the intercept equals [1/sum of initial concentration of all sulfur-containing compounds in this mixture]. Fig. 8 shows an example of the linear representation between the logarithm of the multiplied concentration of DBT, 4-MDBT, and 4,6-DMDBT as a function of time for the HDS reaction over the MS catalyst. The slope of this linear line represents the sum of the pseudo-rst order rate constants for all sulfur-containing compounds as described in Eq. (4). One may safely assume that under the present reaction conditions, a combined rst-order reaction for some representative sulfurcontaining components ts the second-order equation reasonably (Figs. 5b and 8). Although this assumption is limited to exist under certain circumstances only, one can use it to deduce some useful conclusions on this matter. During the manipulation of tting these models to match the experimental results using the Mathcad software program, it was noticed that the half-life estimated from the second-order empirical equation was not very different from the average half-life estimated from the individual rst-order plot of these components. The result is described in Table 5. The following approximation can thus be suggested:

dC Ai ki C Ai dt C Ai C Ai expki t Ln  C Ai C Ai  ki t

1 2 3

where CAi is the concentration of component i at reaction time t and CAio is the initial concentration of component i. The overall rate is the algebraic sum of the rates for the reaction of the individual species. Combining the pseudo-rst-order equations of the three selected sulfur-containing components, for instance, yields the following:

t1=22nd % t 1=21st

10

Ln (S content as DBTx4MDBTx46DMDBT

Ln

 C A1 C A2 C A3 k1 k2 k3 t k1st t C A1 C A2 C A3

10 Experimental Fitted 8

The half-life of the reaction for the combined components is estimated to be:

n Ln2 k1 t 1=21 k2 t 1=22 k3 t 1=23


Assuming

 t1=21 t 1=22 t1=23 . . . t1=2n t 1=21st n


Then

t 1=21st

n Ln2 k1st

50

100

150

200

250

where n is the number of all sulfur-containing components in the feedstock and k1st is the sum of pseudo-rst-order rate constants of each sulfur-containing compound in the real feedstock. The change in combined concentrations of DBT, 4-MDBT, and 4,6-

Time, min
Fig. 8. Pseudo-rst-order kinetics of hydrodesulfurization of multiplied content of DBT, 4-MDBT, and 4,6-DMDBT in gas oil over MS catalyst at 340 C and 3 MPa H2. The theoretical tting was fullled according to Eq. (4).

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If the total number of sulfur-containing components in the real feedstock is known, then the sum of the apparent pseudo-rst-order rate constants of all sulfur-containing components in the real feedstock can be estimated according to Eq. (7) (the empirical second order manipulation). Therefore, an intrinsic kinetic interpretation of the observed data can be evaluated. The HDS rate constant of CMS for total sulfur removal was an order of magnitude higher than that of MS or the conventional catalyst, irrespective of the basis on which these activities were estimated. This indicates an existence of potential synergy between Co- and Mo-sulde phases in case of CMS catalyst [41]. However, when considering the activity according to the unit surface area, the CMS catalyst was approximately 85-fold more active than the commercial CoMo/Al2O3 catalyst. On the other hand, there is a difference in the relative catalytic performance in the HDS of pre-treated gas oil and the combination of DBT, 4-MDBT, and 4,6-DMDBT in the pre-treated gas oil (Fig. 9). The CMS catalyst exhibits a higher relative catalytic activity for the HDS of pretreated gas oil than that for the representative aggregate of DBT, 4-MDBT, and 4,6-DMDBT. Thus, one should be careful in terms of ranking catalysts based on the criteria of their activities for the HDS reaction when utilizing model sulfur-containing components alone. The present result reveals that there is still room for further development of the unsupported metal-sulde catalysts to display more superior activity. While the CMS catalyst shows the highest activity among other catalysts for the conversion of individual sulfur-containing components, its performance for the HDS of pre-treated gas oil is much more pronounced. This suggests that in the evaluation of the relative performance of catalysts for the HDS reaction, it is recommended to extend the investigation to the real feedstock and not to rely solely on investigating model sulfur-containing components. The unsupported catalysts perform the HDS reaction mainly via the hydrogenation route [9,13]. Thus, a catalyst of potential hydrogenation activity with tolerance for nitrogen inhibition may be promising for fullling ultra-deep HDS of real feedstock. The results in Table 4 show that a considerable amount of sulfur in gas oil exists as DBT, 4-MDBT, and 4,6-DMDBT. The sulfur content in these components represents approximately 25% of the all sulfur content in the pre-treated gas oil before reaction. Interestingly, even after the HDS reaction, the sulfur content represented by these components still constitutes from 13% to 24% of the total sulfur. The rest of this percentage is supposed to be comprised from the derivatives of such sulfur species. This result indicates that at high HDS conversion, the least refractory sulfur-containing compounds are dominating. These results stress the importance of

fully understanding the reaction mechanism of these components. The marked differences in reactivities of these sulfur-containing compounds in gas oil have important implications on catalyst selection and optimum reaction conditions for performing ultradeep HDS. As we move toward ultra-low sulfur fuel, the chemistry should be focused and directed toward investigating in more detail the reaction behavior of these compounds. 5. Summary and conclusions The HDS of gas oil was studied over two synthesized unsupported catalysts, that is, MS and CMS and a commercial CoMo/ Al2O3 catalyst under typical operating conditions. The data show that the nanosized CoMo-sulde catalyst was the most active among the catalysts studied. The decrease in total sulfur content in gas oil during the HDS reaction with reaction time was found to t pseudo-second-order kinetics reasonably well. The HDS of certain individual sulfur-containing components in gas oil exhibits pseudo-rst-order kinetics. However, the reaction of the overall mixture shows pseudo-second-order kinetics. The data obtained were analyzed based on a suggested kinetic model approach. The results also imply that a catalyst with potential hydrogenation activity is preferred to the traditional CoMo-based catalysts to achieve gas oil of ultra-low sulfur content. The obtained data suggest that a more developed unsupported nanosized metal-sulde catalyst can provide promise for superior activity in the HDS reaction. References
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18

Ratio of k2nd /k2nd (CoMo/Al2O3)

15 Real feedstock 12 9 6 3 0 CMS MS CoMo/Al2O3 DBT+4-MDBT+4,6-DMDBT

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