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Applied Catalysis A: General 243 (2003) 207–214

Inhibition effects of nitrogen compounds on the
hydrodesulfurization of dibenzothiophene: Part 2
Georgina C. Laredo a,∗ , Efra´ın Altamirano b , J. Antonio De los Reyes b
a

Instituto Mexicano del Petróleo, Programa de Tratamiento de Crudo Maya. Eje, Central Lázaro Cárdenas 152,
07730 San Bartolo Atepehuacan, Mexico
b Depto. de Ingenier´ıa de Procesos e Hidráulica, División de Ciencias Básicas e Ingenier´ıa,
Universidad Autónoma Metropolitana-Iztapalapa, Av. Michoacán y La Pur´ısima, 09340 Vicentina, Mexico
Received 23 January 2002; received in revised form 23 May 2002; accepted 24 May 2002

Abstract
The inhibiting effect of certain basic and non-basic nitrogen compounds on the hydrodesulfurization of dibenzothiophene,
at conditions commonly used in the hydrotreatment of diesel feedstocks, has been experimentally determined. Nitrogen
compounds studied herein are indole, indoline and o-ethylaniline. The inhibition behavior of these compounds is highly
non-linear, showing strong inhibition at concentrations as low as 28 ppm (as nitrogen). The inhibiting effect of the non-basic
compound, indole, was found to be comparable to that of the basic compounds, indoline and o-ethylaniline, although indoline
and o-ethylaniline show a slightly higher inhibiting strength than their parent compound, indole. This behavior suggests
that the coverage of active sites by nitrogen compounds is established on the early stages of the reaction and remains nearly
constant throughout the experiment, and shows that their inhibiting behavior is due to a strong initial adsorption of the nitrogen
compound and a slow kinetics of desorption, rather than to the hydrogenation of the non-basic species to basic ones.
The experimental data for dibenzothiophene hydrodesulfurization in the presence of indole, indoline and o-ethylaniline
was quantitatively represented by a modified Langmuir–Hinshelwood type rate equation.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hydrodesulfurization (HDS); Hydrodenitrogenation (HDN); Hydrotreatment (HDT); Hydrogenation; Inhibition; Reaction kinetics;
Dibenzothiophene; Nitrogen compounds; Indole; Indoline; o-Ethylaniline

1. Introduction
Nitrogen compounds naturally occurring in atmospheric gas oil (AGO) and light cycle oil (LCO),
used as feedstocks for diesel fuel production, are traditionally considered as being responsible for color
and gum formation. Moreover, they have been identified as strong inhibitors of the HDS reactions during
the hydrotreatment process, [1,2] even when they
∗ Corresponding author. Tel.: +52-55-3003-6615.
E-mail addresses: jarh@xanum.uam.mx, glaredo@imp.mx
(G.C. Laredo).

are present in very low concentrations [3]. Usually,
the basic nitrogen compounds have been considered
stronger inhibitors for the HDS reactions than the
non-basic moieties [1,2]. However, strong inhibition
of these reactions by non-basic nitrogen compounds
has been observed, either due to hydrogenation reactions occurring during this process, that lead to
the formation of basic species [4,5], or to a strong
adsorption of the non-basic compounds over the support surface [6–8]. For carbazole, Nagai and Kabe
[4] and LaVopa and Satterfield [9] reported a strong
inhibiting effect on the thiophene and dibenzothiophene hydrodesulfurization reactions, comparable to

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The high value of the adsorption characterizing carbazole was attributed to products of a rapid hydrogenation converting it to basic compounds. 0.3 wt.3.9%) and hydrogen sulfide (99%+) were obtained from Infra. Different sizes of catalyst particles (150. 10 wt. the temperature was increased to 280–320 ◦ C and hydrogen was introduced until the required pressure (5. 2.% Mo) with the following characteristics: bulk density 0. Furimsky and Massoth [2] have reported a long-time adsorption of this compound. Dibenzothiophene was obtained from Fluka (98%+) and the nitrogen compounds from Merck (98%+). As for indole.39 wt.6–17. equivalent to 28–323 ppm as nitrogen. Laredo et al.3 g. indoline and o-ethylaniline) was added at concentrations of 1. Analytical 2. the main objective of this work was to determine the inhibiting effect of indole and its hydrogenation products indoline and o-ethylaniline on the dibenzothiophene hydrodesulfurization reaction at pressures and temperatures commonly used in the hydrotreatment of diesel and at sulfur and nitrogen concentrations relevant to deep hydrodesulfurization. and HDS–HDN experiments were carried out in a 400 ml stirred autoclave (Parr Pressure 2.% Co. [10] reported an inhibiting strength order of indole > quinoline > carbazole.53 ␮m capillary column coated with a non-polar methyl silicone phase (DB-1. Apparatus and procedure HDS. The nitrogen compound (indole.1. 2. A Langmuir–Hinshelwood type equation that quantitatively describes the observed behavior is also provided. Hexadecane (99%) from Aldrich was used as solvent. Experimental For accomplishing product identification in the samples. J & W) was employed.9 mmol/l. The dibenzothiophene conversion showed a first-order behavior when graphing ln[(CDBT )/(CDBT )0 ] versus time.C.7–0.00163 mol) was dissolved in 100 ml of hexadecane to a concentration of 0. pore volume 0. 2.5.0163 mol/l).45 cm3 /g. 2. Control of the kinetic regime A set of experiments was performed to check the absence of intraparticle and interphase mass transfer limitations. In a recent work.2. Reactor 4842). sieved to a 149–177 mm size range and sulfided in a fixed bed reactor using a gas mixture of 10% H2 S and 90% H2 by volume at 280 ◦ C for 4 h. with a slow recovery of the catalyst activity for hydrodesulfurization of dibenzothiophene and hydrogenation of naphthalene after its removal from the feed.95 were obtained in all cases. The extrudates were crushed. piperidine and acridine. After purging with nitrogen. The dibenzothiophene hydrodesulfurization rate constants for all the experiments were calculated using the integral method in order to get comparative results. A 30 m × 0. equivalent to 675 ppm of sulfur.77 g/cm3 . Catalyst and reagents 2. a Perkin-Elmer gas chromatograph model Autosystems XL with a flame ionization detector (FID) was used. / Applied Catalysis A: General 243 (2003) 207–214 those of the basic compounds pyridine.% (0. Further. and surface area 150 m2 /g.208 G. Kinetic calculations The catalyst used was a CoMo/␥-Al2 O3 commercial catalyst (IMP-DSD-14. The mixture was poured into the autoclave and the catalyst (1 g) was transferred to the reactor avoiding exposure to air. a 27 kcal/mol value was obtained for the apparent activation energy of the dibenzothiophene hydrodesulfur- . The typical procedure was as follows: dibenzothiophene (0. 500 and 840 ␮m) were tested and the results indicated that a kinetic regime was established in all cases.1 MPa) was reached. Dry hydrogen (99. Laredo et al. Reaction pressure was maintained by adding hydrogen during the experiment. Correlation coefficients higher than 0. In order to find out if this unusual behavior is due to the strong adsorption of the non-basic parent compound or to the basic nature of the hydrogenation products resulted during the hydrotreatment process. The amount of nitrogen compound needed to form a monolayer over the catalyst surface was calculated to be 30 ppm as nitrogen [11].4. The slope and the correlation coefficient were calculated via least-squares fitting. Reaction time measurement started when the agitation (1500 rpm) began.

G.1 MPa.13] with DBT being converted to biphenyl (BP) and cyclohexylbenzene (CHB) (Fig. [10] from a Langmuir–Hinshelwood equation [14–16]. Results and discussion 3. 3.1 MPa. (a) Products distribution as a function of time.1. showing that we were working in the absence of diffusional limitations. and the kinetic equation used was the result of a simplification described previously in Laredo et al. / Applied Catalysis A: General 243 (2003) 207–214 ization reaction in the 280–320 ◦ C temperature range. (b) First-order behavior for DBT conversion. Biphenyl (䉬). Dibenzothiophene hydrodesulfurization reaction Initial experiments were undertaken to verify the dibenzothiophene hydrodesulfurization behavior at 209 320 ◦ C and 5. 1a). The results show the typical product distribution already reported elsewhere [12.C. Dibenzothiophene hydrodesulfurization follows a first-order behavior. . giving: rHDS = kDBT CDBT (1) Fig. cyclohexylbenzene (䉱). 1. without nitrogen compounds. Dibenzothiophene hydrodesulfurization over a CoMo/Al2 O3 catalyst at 320 ◦ C and 5. Laredo et al. using hexadecane as solvent.

o-ethylaniline (OEA). Indole hydrodenitrogenation 3. hexadecane as solvent is shown in Fig. was 1. 3. 17. octahydroindole (OHIN). Indole (IND). This value will be used as a reference for the results obtained in the experiments where this reaction was inhibited by nitrogen compounds. This product distribution agrees with previous mechanistic indole hydrodenitrogenation studies (Fig. 3.18]. o-ethylcyclohexylamine (OECHA). Inhibition by nitrogen compounds The product distribution from the indole hydrodenitrogenation at 320 ◦ C and 5. .C.210 G. ethylbenzene (EB) and ethylcyclohexane (ECH). Laredo et al. ethylbenzene (EB). The products identified by GC/MS were indoline (HIN).2. indoline (䊏). ethylcyclohexane ( ).7 mmol/l). The value obtained for kDBT at 320 ◦ C (Fig. previously described in the experimental section. Indole (䉬).27 × 10−2 min−1 . ethylbenzene (䊐). Hydrodenitrogenation of indole: product distribution as a function of time at 320 ◦ C and 5.1 MPa over CoMo/Al2 O3 .1 MPa in the Fig. ethylcyclohexane (ECH).1 MPa. 3) [17. o-ethylaniline (). / Applied Catalysis A: General 243 (2003) 207–214 Fig. 2 (indole concentration. Reaction pathways for the HDN of indole suggested by Zhang and Ozkan [18]. 1b) using the integral method. 2. ethylcyclohexene (ECHE). indoline (HIN). versus time using The dibenzothiophene hydrodesulfurization reaction was carried out at 320 ◦ C and 5.3. o-ethylaniline (OEA).

16 6.81 28 57 112 224 323 0.1 MPa and 320 ◦ Ca Indole Indoline Initial concentration  kDBT × 10−2 (mmol/l) (ppm)b (min−1 ) 1.11 5.28 0.57 3.41 0.98 0. 4. The results of these experiments were fitted to a pseudo-first-order rate equation.96 0.38 0. / Applied Catalysis A: General 243 (2003) 207–214 211 Table 1 Inhibiting effect of nitrogen compounds on DBT HDS at 5. Therefore. presence of different concentrations of indole.95 0. Dibenzothiophene hydrodesulfurization inhibition factors for pure nitrogen compounds evaluated at 5. Indole ( ).33 0.45 0. tailing off at higher concentrations. the inhibiting strength increased in the following order: indole < indoline < o-ethylaniline Although the differences between them are small.20 12.19 R2 0.27 0.0163 mol/l. 4): Φ=  kDBT − kDBT kDBT (3) The inhibiting effect increases as the nitrogen concentration increases.98 0.99 0.98 0.C.98 o-Ethylaniline Initial concentration  kDBT × 10−2 (mmol/l) (ppm)b (min−1 ) 1.97 0.55 0.23 0.87 28 55 109 217 313 0.99 12. 675 ppm as sulfur.50 0.41 17.99 Initial concentration  kDBT × 10−2 (mmol/l) (ppm)b (min−1 ) 1.98 0.43 17. indoline and o-ethylaniline.57 3. An inhibition fac- tor (Φ) was calculated in order to show the degree of inhibition in each experiment (Fig.20 17. the dibenzothiophene hydrodesulfurization behavior for this set of experiments could be appropriately represented by the following equation:  rHDS = kDBT CDBT (2)  where kDBT is the pseudo-first-order rate constant for the dibenzothiophene hydrodesulfurization reaction inhibited by nitrogen compounds.95 in all cases (Table 1). As nitrogen.98 0. with correlation coefficients (R2 ) better than 0.22 R2 0.98 0. indoline (䊏). o-ethylaniline ( ).95 0.G.28 a b R2 0.35 0.57 3.05 6.1 MPa and 320 ◦ C.95 DBT initial concentration 0. Laredo et al.95 0.57 28 56 110 221 318 0.10 12.45 0. .31 0. In this work. the slightly higher inhibiting effect of indoline and Fig.

the variation in the nitrogen compound concentration along time was not considered in the development of the model. o-ethylaniline ( ).4.e. i. Kinetic model for inhibition by indole. indoline (䊏). 3. because if that was the case. probably due to the slow kinetics of desorption of these compounds [2].C. the formation or disappearance of basic compounds or the degree of organic nitrogen removal. Therefore.212 G. The inhibiting strength does not seem to be affected by the conversion of the parent nitrogen compound. CN the initial nitrogen compound concentration (mol/l) and n is the fitting exponent.5 are shown in Fig. suggests that the indole inhibiting effect could not be attributed only to hydrogenation reactions converting it into basic compounds [19. This behavior suggests that the coverage of the available active sites by nitrogen compounds is established in the early stages of the reaction and remains nearly constant throughout the experiment. / Applied Catalysis A: General 243 (2003) 207–214 o-ethylaniline. indoline and o-ethylaniline The excellent representation of the experimental results by a pseudo-first-order rate equation (Table 1) implies that the inhibition effect is approximately constant during each test. the inhibition behavior seems related to the strong adsorption of the specific nitrogen compound directly on the catalyst surface [22–24]. the o-ethylaniline inhibition strength. [10] in a previous paper: rHDS = kDBT CDBT 1 + K N n CN n (4) where KN is the apparent nitrogen compound adsorption equilibrium constant (l/mol) and represents the behavior of all the nitrogen compounds that contribute to the inhibition. all these compounds should have the same strength at the same nitrogen concentration.  The pseudo-first-order rate constant kDBT (Table 1) for dibenzothiophene hydrodesulfurization in the presence of each nitrogen compound is expressed by the following equation:  kDBT = kDBT 1 + K N n CN n (5)  Plots of kDBT /kDBT versus initial concentration of indole. 5. Laredo et al. indoline and o-ethylaniline using a fitting exponent of 0.20]. . Obtention of the adsorption term concentration exponent n on the representation of the dibenzothiophene hydrodesulfurization inhibition by indole ( ). It is noteworthy that Fig. Then. 5. In order to perform kinetic calculations the following model was proposed by Laredo et al. as it has been suggested by Ho [21] and Odebunmi and Ollis [5].

0 4.6 221.5 Apparent adsorption constant KN n (l/mmol)n KN (l/mmol) 0. supporting the validity of the model. (4) and were compared with the experimental data (Fig. The inhibiting effect of the nitrogen compounds included . The corresponding adsorption constants KN for indole.C. 4. the fitting exponent obtained for indole in this set of experiments agrees with the value obtained in a previous work [10].8a 0.26] follow the same trend as the adsorption constants. such as indoline and o-ethylaniline.3 Gas-phase basicity (kcal/mol) [26] n 215.14 1. the inhibiting effect does not seem to be attributable to the basic strength of the nitrogen compounds because neither the pKa nor the gas-phase basicity values [25. Fig.G.5 0.4 205. / Applied Catalysis A: General 243 (2003) 207–214 213 Table 2 Apparent adsorption constants for the nitrogen compounds Nitrogen compound Indole Indoline o-Ethylaniline a pKa −3. Moreover. in order to verify the agreement of the  model with our experimental results. 6.30 1. according with the results found in this work. indoline and o-ethylaniline are shown in Table 2.9887 0. indoline (䊏). The predicted values are in very good agreement with the experimental data in the whole range of nitrogen compounds concentrations tested.88 R2 0. o-ethylaniline ( ). Comparison between experimental and calculated pseudo-first-order rate constants for dibenzothiophene hydrodesulfurization inhibited by indole ( ).5 0.9707 0.74 1. The highest adsorption constant KN was obtained for o-ethylaniline (1. 6). Laredo et al. which was a stronger inhibitor than indole and indoline. Finally. Conclusions The inhibiting effect of the non-basic nitrogen compound indole on the dibenzothiophene hydrodesulfurization reaction is comparable to that of basic nitrogen compounds. kDBT values were calculated using Eq.86 1.9914 Estimated from available data [26].37 0.88 l/mmol).6 5.

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