Sie sind auf Seite 1von 14

Applied Catalysis A: General 207 (2001) 407420

Catalytic hydrotreating of middle distillates blends in a xed-bed pilot reactor

Gustavo Marroqu n-Snchez a , Jorge Ancheyta-Jurez a,b,

Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas 152, Mxico 07730 DF, Mexico b Instituto Politcnico Nacional, ESIQIE, Mxico 07738 DF, Mexico Received 24 March 2000; received in revised form 12 June 2000; accepted 18 June 2000

Abstract An experimental study was conducted in a xed-bed pilot reactor in order to evaluate the effect of catalytic hydrotreating on diesel quality by using feedstocks prepared with different amounts of straight run gas oil, kerosene and jet fuel streams. Experiments were carried out at constant reaction pressure and hydrogen-to-oil ratio of 5.3 MPa and 356.2 ml ml1 , respectively. The effect of reaction temperature and liquid hourly space velocity were studied in the range of 613633 K and 1.52.0 h1 , over a commercial Ni-Mo/-Al2 O3 catalyst. The experimental information showed that diesel specications could be reached through single stage hydrotreating of these blends at moderate hydrotreating operating conditions. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Middle distillates; Hydrodesulfurization; Hydrotreating

1. Introduction Catalytic hydrotreating (HDT) plays an important role in the modern oil rening industry. The HDT process ranks in importance with other petroleum rening processes, such as catalytic cracking and reforming. The uses of the HDT process include predominantly the desulfurization of middle distillates (kerosene, diesel fuel and jet fuel). HDT is a catalytic process in which a number of reactions are involved, i.e. hydrogenolysis, by which CS, CN or CC bonds are cleaved and hydrogenation of unsaturated compounds. The reacting conditions of the HDT process vary with the type of feedstock; whereas light oils are easy to desulfurize, the desulfurization of heavy oils is very difcult.
Corresponding author. Fax: +52-5-587-3967. E-mail address: (J. Ancheyta-Ju arez).

In view of the new diesel specications introduced around the world (Table 1) [15], the demand for high-quality middle distillates has grown signicantly over the past decade [6]. Gas oils deep hydrodesulfurization has achieved much attention since the tolerated sulfur content in diesel fuel is being lowered more and more. It becomes necessary to remove sulfur from the compounds that are the most difcult to desulfurize, which are higher molecular weight dibenziothiopenes (DBT) that contain side chains in positions that limit the access of the molecule to the active sites on the catalyst, such as 4-methyl DBT and 4,6-dimethyl DBT [7]. Straight run gas oil (SRGO) obtained from atmospheric distillation units remains the main source of diesel fuels, and in some cases, the light cycle oil (LCO) produced in uid catalytic cracking units (FCC) is frequently used as HDT feedstock. The

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 6 8 3 - 9


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Table 1 Specications for diesel fuels in different countriesa Property API gravity Flash point, K Viscosity @ 313 K, cSt Nitrogen, wppm Sulfur, wppm Aromatics, vol.% PNA, vol.% Cetane number, min Cetane index, min ASTM distillation, K IBP 10 vol.% 50 vol.% 90 vol.% 95 vol.% EBP

Mexico PEMEX (a) >32 >318 1.94.1 500 30 48 48

US EPA (a) >30 1.94.1 500 35

US CARB Sweden (a) class I (b) 3339 >327 2.04.1 10 500 10 1.4 wt.% 48 41.145.4 1.24.0 10 5 0.02 50 444489 477527 516566 561594 577622 453

UK (c)

Germany (d)

Europe (e) >36

Europe (f) >36

Worldwide fuels charter 3741.1

3841.1 >37




50 (10)b 10 wt.% <2 wt.% 55 54



611 wt.% 16 wt.% 51 5458

<30 15 2 >55 >52

548 618 611 639

558 573





<593 <613 <623

(a) 1993, (b) 1992, (c) 1998, (d) 2001 (e) 2000, (f) values proposed for year 2005. b 2003.

problem of LCO processing is its low cetane number and higher density, sulfur, nitrogen and aromatics, which adversely affect the quality of the resulting diesel fuel [8]. In addition, the most refractory sulfur compounds are expected to be present in a greater concentration in streams, such as LCO [7]. Because of the increasing demand of diesel fuel, reners are looking for HDT strategies to achieve the required sulfur and aromatics contents. However, the use of conventional HDT catalysts for deep desulfurization of SRGO in traditional hydrotreating units would require severe operating conditions. Such changes have the following impact in commercial units [2]: An increase in reactor temperature will reach low sulfur content in the product. Whereas this increase will result in severe color degradation and in shorter catalyst cycle length. A decrease in space-velocity will reduce the plant capacity, and in order to maintain the existing production capacity, new HDT reactors will have to be added. An increase in hydrogen partial pressure would be favorable for sulfur and aromatics contents reduction and color improvement. However, the existing plants do not allow for an increase of total pressure due to existing physical constraints of maximum total pressure.

It is well known that the boiling range of the feedstock and mainly the heaviest fractions have a very large impact on the required HDT operation conditions. As the average boiling point increases, the concentration of sulfur compounds also increases and the HDS reactivity is reduced. Because of this, another possibility for achieving a high-quality diesel production is to incorporate middle distillates (kerosene or jet fuel) together with the SRGO as HDT feedstock. However, the amount of these distillates in the blend needs to be optimized in order to obtain the required quality in the product using traditional HDT units, catalysts and operating conditions. The objective of the present study is to evaluate the effect of the inclusion of middle distillates (kerosene and jet fuel) together with SRGO as HDT feedstocks. In addition, the effect of reaction temperature and liquid hourly space velocity (LHSV) are also studied in order to dene the best operating conditions to achieve the required product quality. 2. Experimental 2.1. Middle distillates The properties of the three streams used for preparing the HDT feedstocks (SRGO, kerosene and jet fuel) are presented in Table 2.

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420 Table 2 Middle distillates and blends properties Properties API gravity Flash point, K Viscosity @ 313 K, cSt Nitrogen, wppm Sulfur, wt.% Aromatics (FIA), vol.% Aromatics (SFC), wt.% Mono-, wt.% Di-, wt.% Tri-, wt.% Cetane number ASTM distillation, K IBP 10 vol.% 50 vol.% 90 vol.% FBP
a b


SRGO 33.38 333 4.10 317 1.21 26.4 31.70 14.82 13.42 3.46 54.1 429 543 586 619 637

Ka 40.16 331 1.76 47 0.67 21.8 24.60 17.09 7.51 0.00 48.0 409 474 507 536 554

JFb 47.12 317 0.99 9 0.21 19.0 21.04 20.04 1.00 0.00 42.8 417 442 461 483 504

B-1 41.84 321 1.71 103 0.58 21.4 24.36 18.04 5.59 0.73 47.5 409 452 491 578 616

B-2 39.75 323 2.02 142 0.71 22.3 25.90 17.25 7.47 1.18 48.9 414 459 516 599 624

B-3 38.57 328 2.21 179 0.81 23.2 26.85 16.36 8.72 1.77 50.7 427 471 532 600 626

B-4 37.15 328 2.73 207 0.92 23.9 28.29 16.20 10.21 1.88 50.9 429 475 548 606 630

B-5 36.51 335 3.01 227 0.97 24.2 28.37 15.72 10.52 2.13 51.9 418 497 555 609 631

Kerosene. Jet fuel.

These middle distillates were derived from a crude oil with the following properties: 29.42 API, 2.16 wt.% sulfur, 1848 wppm nitrogen, 6.25 wt.% Ramsbottom carbon, 4.9 wt.% asphaltenes in C7 , and 22 and 111 wppm of Ni and V, respectively. It can be observed from Table 2 that the three streams are representative middle distillates (API gravity: 33.38 SRGO, 40.16 kerosene, 47.12 jet fuel). Kerosene and jet fuel do not present aromatics with three rings, inclusive the jet fuel has a very low content of di-aromatics (1.0 wt.%). However, they exhibit a higher mono-aromatics content compared to SRGO. The total aromatic content is high in SRGO because it increases with the boiling point of the fraction. The following blends were prepared with SRGO, kerosene and jet fuel streams: B-1: 20 vol.% SRGO, 30 vol.% kerosene and 50 vol.% jet fuel. B-2: 33.33 vol.% SRGO, 33.33 vol.% kerosene and 33.33 vol.% jet fuel. B-3: 40 vol.% SRGO, 40 vol.% kerosene and 20 vol.% jet fuel. B-4: 60 vol.% SRGO, 20 vol.% kerosene and 20 vol.% jet fuel. B-5: 50 vol.% SRGO, 50 vol.% kerosene and 0 vol.% jet fuel.

The physical and chemical properties of these blends are also shown in Table 2. They are classied in an increasing amount of heteroatoms (i.e. 0.580.97 wt.% sulfur for B-1 and B-5, respectively). Fig. 1 shows the variation of sulfur and nitrogen contents as a function of API gravity for the different blends. It can be seen that the higher jet fuel content (B-1) the higher the API gravity and hence the lower the heteroatoms content. 2.2. HDT catalyst and presulding conditions The hydrotreating catalyst used in the present study was a Ni-Mo/-Al2 O3 commercial available sample and its properties are presented in Table 3. This catalyst showed a MoO3 /NiO ratio of 4.47. After loading the catalyst, the reactor pressure was increased from atmospheric to 6.9 MPa (30% higher than typical reactor pressure) in order to be sure of the airtightness of the system. This condition was kept during 2.5 h. Once the reactor was verify to be hermetic, the reactor pressure was decreased to 5.3 MPa. The temperature of the reactor was increased from ambient to 503 K at a heating rate of 30 K h1 in the presence of hydrogen (99.8% purity) at a ow rate of 150 l h1 .


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Fig. 1. Sulfur and nitrogen contents as a function of API gravity.

The catalyst was in-situ presulded with a desulfurized naphtha (specic gravity of 0.752, <0.5 wppm sulfur and boiling range of 369466 K). The naphtha was contaminated with 0.8 wt.% CS2 at 5.3 MPa, a hydrogen-to-oil ratio of 356.2 ml ml1 , at 503 K, a weight hourly space velocity (WHSV) of 3 h1 , 13 h, to ensure complete catalyst presulding. 2.3. Pilot plant runs The HDT studies were conducted under steady-state operation in a xed-bed hydrotreating pilot plant (Fig. 2).
Table 3 Catalyst properties Property Physical properties Shape Diameter, mm Length, mm Surface area, m2 g1 Pore volume, ml g1 Bulk density, g ml1 Chemical properties MoO3 , wt.% NiO, wt.% P, wt.% Na2 O, wt.% Ni-Mo catalyst Extrudate trilobe 2.5 6.1 176 0.51 0.75 10.5 2.35 1.35 0.05

The isothermal reactor is designed as a tube with an inside diameter of 2.54 cm and a overall length of 143 cm (Fig. 3). The length of reactor is subdivided in three sections. The rst section was packed with inert particles and was used to heat up the mixture to the desired reaction temperature and to provide a uniform feedstock distribution. The following section contained the Ni-Mo/-Al2 O3 HDT catalyst. The exit section was also packed with inert particles. The catalyst (75 ml) were diluted with equal volume of inert -alumina in order to maintain a ratio of the volume of catalyst to that of diluent at a constant value of 1.0. This inert was considered to be of negligible activity and did not contribute catalytically to the hydrotreating reactions, and it was prepared to have similar size as the catalyst commercial sample. The use of nonporous inert is recommended and widely accepted in the literature to handle the problems in testing catalyst having commercially applied size and shape, such as poor wetting of catalyst, wall effect, backmixing of liquid, and external mass transfer limitations. Another benecial effect of catalyst bed dilution is that temperature homogeneity in the bed is improved and that the chances of temperature runaway are diminished in the case of strongly exothermic reactions. Thus, the hydrodynamics of the owing uids will be mainly dictated by the packing of

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420



G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Fig. 3. Isothermal reactor.

small inert particles, whereas the catalytic conversion behavior is that of the catalyst in the actual size [9]. The reactor temperature was maintained at the desired level (613, 623 or 633 K) by using a three-zone electric furnace, which provided an isothermal temperature along the active reactor section. The catalytic bed temperature was measured during the experiments by three thermocouples lo-

cated in a thermowell mounted at the center of the reactor. The temperature prole was measured at the middle of each experiment by a movable axial thermocouple located inside the reactor. The greatest deviation from the desired temperature value was about 34 K. Three typical temperature proles at 613, 623 and 633 K are shown in Fig. 3. It can be observed that an increase

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420


in the reaction temperature increased the temperature differential along the reactor due to the exothermicity of the reactions. 2.4. Operating conditions in the pilot reactor Once the catalyst sulding was completed, the temperature of the reactor was increased to the desired reaction temperature and the feedstock and hydrogen were passed at the required rates. The hydrodesulfurization of the ve blends was carried out at the following operating conditions: reaction temperature of 613, 623, and 633 K, and LHSV of 1.5 and 2.0 h1 . Reaction pressure and hydrogen-to-oil ratio for all runs were 5.3 MPa and 356.2 ml ml1 , respectively. It was used pure hydrogen in a once-through mode. Product samples were collected at 48 h intervals after allowing a 2 h stabilization period under each set of conditions and mass balances for each run were in the range 1005% [10]. 2.5. Analysis of products Physical and chemical properties were determined with the following methods: API gravity: ASTM D-287. Total sulfur: ASTM D-4294. Total nitrogen: ASTM D-4629. Flash point: ASTM D-93. Cinematic viscosity: ASTM D-445. Distillation curve: ASTM D-86. Cetane number: ASTM D-613.

has been chosen by ASTM to replace the FIA method for determination of aromatic hydrocarbons content in diesel fuels. Besides the FIA method does not give the aromatics distribution, it is applied only for fuels with nal boiling point (FBP) less than 588 K, and SFC method is valid for fuels in the boiling range of 473673 K [11].

3. Results and discussion 3.1. Effect of reaction temperature and space-velocity on diesel quality The effect of reaction temperature on product quality at LHSV of 2.0 h1 , 5.3 MPa total pressure and 356.2 ml ml1 hydrogen-to-oil ratio is presented in Fig. 4 for the ve HDT feedstocks. The product quality shown the classical behavior when the temperature is increased in the range 613633 K, that is a decrease in sulfur, nitrogen and aromatics, and hence an increase in cetane number. It should be mentioned that the reversibility of the aromatics saturation reaction was not observed in this study, which has been reported in the literature [12] to be at higher temperatures (>633 K at 5.3 MPa). The effect of space velocity (LHSV) on product quality at 633 K reaction temperature, 5.3 MPa total pressure and 356.2 ml ml1 H2 /oil ratio is presented in Fig. 5 for the ve feedstocks. A decrease in LHSV from 2.0 to 1.5 h1 resulted in improved product quality (a reduction in sulfur, nitrogen and aromatics contents, and an increase in cetane number). It can be observed from Figs. 4 and 5 that the ve feedstocks reach less than 380 wppm sulfur, 53 wppm nitrogen and 21.2 vol.% aromatics, in the range of temperature 613633 K and LHSV of 1.52.0 h1 . Cetane numbers were higher than 49 for all feedstocks. Very low sulfur, nitrogen and aromatics contents were obtained with feedstock B-1 (<180 wppm, <9 wppm and <17.7 vol.%, respectively) due to the high jet fuel content (50 vol.%). The best aromatic conversion was obtained at the most severe combination of temperature and LHSV (633 K and 1.5 h1 ) for the ve feedstocks. For B-1 feed, the reduction in aromatics was from 21.4 to 15.5 vol.% at these conditions, corresponding to an

Aromatics content in feed and products was measured by uorescent indicator adsorption (FIA) (ASTM D-1319), and by supercritical uid chromatography (SFC) (ASTM D-5186), which determines aromatics distribution (mono-, di-, tri- and poly-) in wt.%. The FIA method has been prescribed by the Environmental Protection Agency as a standard method for specifying aromatics in diesel fuel, which gives the total aromatics content in vol.%, however, it does not give breakdown of aromatics distribution. On the other hand, the environmental legislation about the aromatics content in diesel fuels has led to an increased fundamental interest in the detailed nature of aromatic fractions. In this sense, the SFC method


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Fig. 4. Effect of reaction temperature on product sulfur, nitrogen, aromatics and cetane number at 2.0 h1 LHSV, 5.3 MPa total pressure and H2 /oil ratio of 356.2 ml ml1 . () B-1; () B-2; ( ) B-3; () B-4; () B-5.

increase of 3.1 units in cetane number. This behavior at high temperature and low space-velocity is because the aromatics saturation and cetane number improvement require high severity for CC bond scission to take place from naphthenes to mono-aromatic molecules. Feedstocks B-4 and B-5 presented aromatics higher than 20 vol.% at low temperature and high space velocity (613 K and 2.0 h1 ). This result was expected since B-4 and B-5 feeds contain high content of SRGO, 60 and 50 vol.%, respectively, which is the higher aromatic concentration stream used for preparing the HDT feedstocks (26.4 vol.%). The ash point and viscosity of the hydrotreated product decreased, while API gravity increased as the

reaction temperature was increased and the LHSV was decreased. The values of these diesel properties changed in the following ranges: ash point, 338365 K; viscosity, 1.932.86 cSt, and API gravity, 3842.9 . The boiling range of the hydrotreated products presented the following ranges: IBP, 448483 K; 10 vol.%, 460506 K; 30 vol.%, 474525 K; 50 vol.%, 491544 K; 70 vol.%, 519567 K; 90 vol.%, 571600 K, and FBP: 610625 K. The results of the present studies reveal that hydrodesulfurization is considerable inuenced by reaction temperature and space velocity, and for a given feedstock, low-sulfur diesel fuel (500 wppm max) can

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420


Fig. 5. Space-velocity effect on product sulfur, nitrogen, aromatics and cetane number at 633 K, 5.3 MPa and H2 /oil of 356.2 ml ml1 . () B-1; () B-2; ( ) B-3; () B-4; () B-5.

be achieved by varying one of these process parameters. 3.2. Aromatics distribution in diesel fuels 3.2.1. FIA and SFC methods A plot of total aromatics as measured by FIA and SFC methods is presented in Fig. 6. It can be observed that aromatics calculated by SFC (in wt.%) are always greater than those evaluated by FIA method (in vol.%). This difference becomes higher at high aromatic contents. A lineal relationship, which is also shown in Fig. 6, was found between the aromatic contents evaluated

with these two methods with correlation coefcient R2 =0.97. 3.2.2. Aromatics distribution Aromatic compounds can be divided into four categories [13]: (1) mono-aromatics, (2) di-aromatics, (3) tri-aromatics, and (4) polycyclic aromatics or poly-nuclear aromatics (PNA) with four or more condensed benzene rings. Mono-, di- and tri-aromatics are more common in middle distillates, whereas PNA are found in the heavy fractions [13,14]. This was conrmed in this work since all the HDT feedstocks showed very low contents of aromatics with three rings (Table 2).


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Fig. 6. Comparison of methods for determining percent of aromatics. () Feedstock; () hydrotreated products.

Aromatics saturation in HDT process begins with the partial saturation of multiple-ring aromatics as can be observed in Fig. 7 [15]. However, the mono-aromatics content showed an increase as the multiring compounds are saturated as can be seen in Fig. 8, where the mono-aromatics for B-4 feedstock had increased from 15.72 wt.% to values higher than 19 wt.%, which is mainly due to the hydrogenation of di- and tri-aromatics, since mono-aromatics are much less reactive than di- or tri-aromatics. Di- and tri-aromatics presented a reduction from 10.21 and 1.88 wt.% to values smaller than 3.0 and 0.45 wt.%, respectively. This behavior conrms that mono-aromatics are signicantly more difcult to saturate, which agrees with experiments reported in the literature with model compounds that suggest that naphthalene and substituted naphthalenes are an order of magnitude more reactive than benzene and substituted benzenes [16]. Aromatics density in feeds and hydrotreated products can be calculated with aromatics content in

wt.% (SFC method), aromatics content in vol.% (FIA method) and feedstock density by means of the following equations: garomatics /goil Aromatics in wt .% (SFC) = Aromatics in vol.% (FIA) mlaromatics /mloil = garomatics mlaromatics mloil goil = aromatics oil (1) (2)

aromatics = oil

Aromatics in wt.% Aromatics in vol.%

It should be mentioned that the evaluation of aromatics density with Eq. (2) depends on the accuracy of experimental determination of total aromatics by FIA and SFC methods. SFC method has shown good accuracy and FIA method presents poor accuracy for determining aromatics in diesel fuels. The accuracy of FIA method for diesels having end boiling point (EBP) higher than 588 K has not been yet determined [11].

Fig. 7. Aromatics saturation model.

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420


duced as the severity of the hydrotreating reactions is increased. 3.3. Comparison of hydrotreated product properties with diesel specications All the hydrotreated products obtained in the pilot plant experiments using the ve feedstocks reached the required sulfur content (500 wppm max), cetane number (48 min), and viscosity @ 313 K (1.94.1 cSt for Mexico and 2.04.1 for US CARB legislation), inclusive at the less severe operating conditions (613 K and 2.0 h1 LHSV), as can be seen in Figs. 4 and 5. Aromatics via FIA method presented values smaller than 21.5 vol.% for B-4 and B-5 feedstocks, and smaller than 19.4 vol.% for B-1, B-2 and B-3 feedstocks. The experimental results indicate that at identical operating temperatures very similar sulfur, nitrogen and aromatics contents can be obtained with different feedstocks by adjusting the LHSV (rst two columns of Table 4). The same result could be obtained by operations at the same LHSV but with an increase of the operating temperature, of course, at the expense of catalyst cycle length (third and fourth columns of Table 4). In Table 4 is also shown a comparison of three hydrotreated products (columns 4, 5 and 6) with the CARB diesel specication. It can be observed that all properties reached the required CARB values, except nitrogen and aromatics contents. It should be mentioned that CARB is one of the strictest specications for diesel fuels. The Mexican and US EPA legislations (Table 1) can be easily reached with any of the diesel products obtained by using the ve feedstocks reported in Table 2, within the operating conditions of the present study. In addition, in some cases, the space-velocity may be increased in order to expand the plant capacity. The possibility of increasing the reaction temperature beyond 633 K and of increasing hydrogenation rate is usually limited due to thermodynamic limitations of aromatics hydrogenation. 3.4. Effects of type of feedstock on diesel quality The composition of the feedstock to be treated in a HDT plant will have a signicant impact on the

Fig. 8. Effect of reaction temperature and LHSV on aromatic distribution for B-4 feedstock. () LHSV=1.5 h1 ; () LHSV=2.0 h1 .

Most of the hydrotreated products in this work have EBP higher than 588 K, specially those obtained from feedstocks with high SRGO content. This means that not too much faith should be put on aromatics determination by FIA method. In spite of this, FIA numbers were used together with aromatics by SFC method and Eq. (2) to have an idea of aromatics density. These results are discussed in the following paragraph. Fig. 9 shows the variation of aromatics density in the hydrotreated products, calculated with Eq. (2), as a function of reaction temperature and LHSV for B-1 and B-4 feedstocks. It can be observed that the density of aromatic compounds decreases as the temperature increases and the LHSV is reduced. This conrms that part of heavy aromatics (mostly tri- and di-) are hydrogenated into lower aromatics (mono) and their densities and hence their molecular weights are re-


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

Fig. 9. Effect of reaction temperature and LHSV on aromatics density. () LHSV=1.5 h1 ; () LHSV=2.0 h1 ; () B-1 feedstock; ( ) B-4 feedstock.

unit performance. SRGO obtained from atmospheric distillation remains the main source of diesel fuels. Sometimes, the LCO obtained in FCC or coker gas oils (CGO) are fed to the hydrotreater together with SRGO. Each feed component contains thousands of different molecules, making each unique in its processability. For instance, SRGO is usually the easiest feed to process, and LCO is difcult to treat because of its high sulfur, nitrogen and aromatics contents. These LCO properties adversely affect the quality of the resulting diesel fuel [8].

As the end point of blending components for diesel production increases, the complexity of the heteroatoms increases and hence the hydrodesulfurization rate decrease. Thiophenes are the lightest and most reactive molecules with an unsaturated ring. Benzothiophenes are relatively easy to desulfurize. DBT are harder to desulfurize, but the difculty varies greatly according to their alkyl substitution, for instance DBT substitued at the 4- and 4,6-positions, in particular, are among the most refractory molecules. All of these sulfur compounds can be found in diesel fuels.

Table 4 Comparison of operating condition to reach similar heteroatoms contents with different feedstocks Feedstock Operating conditions Temperature, K LHSV, h1 Product properties API gravity Flash point, K Viscosity @ 313 K, cSt Nitrogen, wppm Sulfur, wppm Aromatics, vol.% Cetane number B-1 633 2.0 42.61 340 1.85 3 82 16.5 50.0 B-2 633 1.5 40.96 345 2.17 5 90 16.8 52.6 B-3 623 2.0 39.66 348 2.45 14 210 18.8 52.0 B-4 633 2.0 38.71 348 2.57 24 207 19.6 54.8 B-4 623 1.5 38.72 354 2.51 26 230 19.1 54.6 B-5 633 1.5 38.45 363 2.65 21 190 18.8 55.6 CARB 3339 327 min 2.04.1 10 max 500 max 10 max 48 min

G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420


Fig. 10. ASTM D-86 distillation curves for SRGO, kerosene and jet fuel.

The concentration of the most difcult to desulfurize species is high in the higher boiling fractions of diesel materials. The level of HDS difculty increases to the point where ring saturation reactions begin to compete with direct sulfur removal as the preferred mechanism for HDS. Tailoring feed components, or diesel feed boiling range can be an effective means of controlling the difculty of diesel HDS [4]. Another option to achieve a high-quality diesel is to use lighter streams, such as kerosene and jet fuel, together with the SRGO in the feedstock to the HDT process in order to have more easier to desulfuize sulfur compounds. With respect to this latter alternative, when the kerosene and jet fuel are blended with SRGO, a considerable reduction in the heteroatoms content in the HDT feedstock is observed. SRGO sulfur and nitrogen contents are 1.21 wt.% and 317 wppm, respectively, and, for instance, for the feedstock having the highest amount of jet fuel (B-1), sulfur and nitrogen contents are 0.58 wt.% and 103 wppm, respectively. Unfortunately, the type and concentration of the different sulfur compounds in the feeds used in this work were not determined, however, as it was stated before, easier to desulfurize compounds are found in lighter fractions, and hence, the rate of hydrodesulfurization increases when these streams are used together with SRGO as HDT feedstock. In spite of this, a good idea about the complexity of sulfur compounds can be obtained by using the

ASTM D-86 distillation curve. Fig. 10 shows the boiling point curves for SRGO, kerosene and jet fuel. The boiling ranges for each stream are: 429637 K SRGO, 409554 K kerosene, and 417504 K jet fuel. According to this gure, jet fuel will exhibit sulfur compounds easier to desulfurize compared to other streams, and its blend with SRGO will also provide a HDT feedstock with less complex and more reactive sulfur compounds. 3.5. Basic approaches to produce low sulfur diesel At present, most of the world reners are either currently producing diesel fuels with 500 wppm sulfur or are investing aggressively to reach this level. However, some countries require a reduction to 50 wppm or to <10 wppm in the near future, years 20032005 (Table 1), and the HDT technologies applied to reduce sulfur in diesel to the 500 wppm level will not be adequate to address the future needs. These new diesel specications will emphasize the need for exible technology solutions that can adapt with the changing regulations. The need to reduce sulfur to <50 wppm represents a considerably increase in the activity of the catalyst. The combination of using more active HDT catalysts, increasing the reaction temperature and reducing the EBP of the feed may provide provisional capability to produce ultra-low sulfur diesel. If the reaction temperature is modied in order to produce diesel containing 50 wppm sulfur in a current HDT


G. Marroqu n-S anchez, J. Ancheyta-Ju arez / Applied Catalysis A: General 207 (2001) 407420

unit producing 500 wppm sulfur diesel, an increase of 2035 K will be required depending of the feed quality [4,5]. This increase in temperature will limit the unit cycle life to an unacceptably short time period. This means that temperature is not an effective solution. Hence, the long term solution will certainly need the addition of reactor volume and quench capability or even the investment in new hydrotreating plants. In addition to sulfur content, future diesel will require signicant reductions in aromatics, density and boiling range together with an increase in cetane number. The optimal reaction pathways to achieve the upgrade objectives will be feedstock dependent and will also need to consider the best utilization of existing renery resources.

Acknowledgements The authors thank Instituto Mexicano del Petrleo for its nancial support. References
[1] D. Dave, G. Hamilton, Harts Fuel Technology and Management, May 1997. [2] S. Kasztelan, N. Marchall, S. Kressmann, A. Billon, Proceedings of the 14th World Pet. Congress, 1994, pp. 1926. [3] F.M. Hibbs, W.H. Keesom, Tech. Bull., UOP, 1995. [4] M. Hunter, A. Gentry, S. Lee, Lucas, C. Olivier, D. Pappal, Paper Presented at the NPRA 2000 Annual Meeting, 2628 March, San Antonio, TX, 2000. [5] W. Shiett, D. Dicamillo, T. Remans, Paper Presented at the NPRA 2000 Annual Meeting, 2628 March, San Antonio, TX, 2000. [6] J.A. Anabtawi, S.A. Ali, M.A. Ali, Energy Sources 18 (1993) 203214. [7] T. Tippett, K.G. Knudsen, B.H. Cooper, Paper Presented at the NPRA 1999 Annual Meeting, 2123 March, San Antonio, TX, 1999. [8] J. Ancheyta, E. Aguilar, D. Salazar, G. Betancourt, M. Leiva, Appl. Catal. A 180 (1999) 195205. [9] S.T. Sie, AIChE J. 42 (12) (1996) 34983507. [10] G. Marroqu n, Reduccin de aromticos en combustible diesel mediante hidrotratamiento catal tico, MSc. Thesis, ESIQIE-IPN, Mxico, 1999 (in Spanish). [11] P. Heinze, W.E. Betts, M. Booth, P. Gadd, F. Giavazzi, H. Guttman, D.E. Hall, R.F. Mayers, R. Mercogliano, R.C. Hetcheson, CONCAWE Report No. 94/58, Brussels, August 1994. [12] B.H. Cooper, A. Stanislaus, P.N. Hannerup, Hyd. Proc. June 1993, pp. 8387. [13] A. Stanislaus, R.H. Cooper, Catal. Rev.-Sci. Eng. 36 (1994) 75. [14] M. Sjgren, H. Li, U. Rannung, R. Westerholm, Fuel 74 (1995) 983989. [15] T. Takatsuka, S. Inoue, Y. Wada, Catal. Today 39 (1997) 6975. [16] M.J. Girgis, B.C. Gates, Ind. Eng. Chem. Res. 30 (1991) 20212058.

4. Conclusions The effect of hydrotreating of SRGOkerosenejet fuel blends on diesel fuel quality has been studied in a pilot reactor over a commercial Ni-Mo/-Al2 O3 catalyst under typical operating conditions. The experimental results showed that the specications in diesel quality can be achieved through single stage hydrotreating of these blends. The maximum sulfur content in diesel fuels (500 wppm) and minimum cetane number (48) can be easily reached at moderate hydrotreating operating conditions. Similar heteroatom contents in the products were observed using the ve feedstocks by adjusting the LHSV or reaction temperatures. A lineal relationship was found between SFC and FIA methods for determining aromatic distribution. This information was used for evaluating the aromatic density, which was employed to show the partial hydrogenation of heavy aromatics into lower aromatics.