Applied Catalysis A: General 233 (2002) 7790

Development of heavy oil hydrocracking catalysts using amorphous silica-alumina and zeolites as catalyst supports
M.A. Ali a, , T. Tatsumi b , T. Masuda c
b a Center for Rening and Petrochemicals, Research Institute, KFUPM, Dhahran, Saudi Arabia Division of Materials and Chemical Engineering, Faculty of Engineering, Yokohama National University, Yokohama, Japan c Advanced Catalysts Research Laboratory, Advanced Technology and Research Institute, Japan Petroleum Energy Center, Kanagawa Science Park, Kanagawa, Japan

Received 12 October 2001; accepted 23 February 2002

Abstract The overall objective of this research work was to prepare hydrocracking catalysts using amorphous silica-alumina (ASA) supports in combination with USY and -zeolites. Three supports: namely silica-alumina, USY and -zeolites were selected to prepare the extrudates using AP-1 as a binder, while two metal pairs: namely NiW and NiMo were loaded on the extrudates through co-impregnation using incipient wetness technique. The catalysts were then calcined at 550 C for 2 h. The catalysts were tested in a xed-bed ow reaction system for their activity, using desulfurized vacuum gas oil (DS-VGO) as a feedstock. The catalytic evaluation results of the catalysts showed that -zeolite alone and in combination with the ASA used in this study, has a potential as a support for developing heavy oil hydrocracking catalysts. A balance of weak and strong acidities of -zeolite provides control cracking, while high surface area and bigger pores of silica-alumina may be useful for producing stable hydrocracking and hydrotreating catalysts. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Silica-alumina; -Zeolite; USY-zeolite; Hydrocracking; Extrudates; Co-impregnation; Incipient wetness method; Desulfurized VGO; Acidity; Surface area; Catalytic evaluation; Fixed bed reaction system

1. Introduction The catalyst used in the hydrocracking process is dual-functional. A hydrocracking catalyst cracks high-molecular-weight hydrocarbons and hydrogenates the unsaturates that are either formed during the cracking step or otherwise present in the feedstock. A typical cracking catalyst consists of silica-alumina with base-metal components. Amorphous silica-alumina (ASA) is viewed as a polymer
Corresponding author. Fax: +966-3-8603586. E-mail address: maali@kfupm.edu.sa (M.A. Ali).

of alumina on a backbone of silica. Crystalline synthetic silica-alumina, known as zeolite, is regarded as a copolymer of alumina and silica with ion-exchange capacity. In the case of ASA, the activity is attributed to both Lewis- and Bronsted-type acid sites. There is distribution of acid strength over the catalyst surface. The strongest sites are not the most favorable because the slow rate of desorption can retard the catalytic reactions. The most favorable sites are the weak ones that are sufciently strong to accomplish the desired chemical reactions. The reactions that occur in hydrocracking can be grouped into two broad classes: these are (1) hydrogenation of olens, aromatic rings,

0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 1 2 1 - 7

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sulfur compounds, nitrogen compounds, and oxygen compounds and (2) cracking of CC bonds. The cracking reactions are slightly endothermic, while the hydrogenation reactions are highly exothermic, and the net heat of reaction for the hydrocracking process is thus exothermic. Thus there is a large adiabatic temperature rise in a commercial hydrocracker, and a major part of the engineering involved in the design of a hydrocracker is the control of this temperature rise. Excessively high temperatures can lead to coke deposition and deactivation of the hydrocracking catalyst. Temperature control is accomplished by the use of cold-recycle-gas quench injected at various points between a series of catalyst beds. Several studies have been conducted using ASA alone and in combination, and comparisons were made with alumina and zeolites as hydrocracking catalyst supports [114]. Some of these studies are described in what follows. A detailed study has been reported for evaluation of hydrodesulfurization (HDS) catalysts having NiW, NiMo, and CoMo metal pairs on a number of supports including alumina loaded with Pt and Pd. The reactions carried out on dibenzothiophene (DBT) and substituted DBT compounds shows that ASA as a support induced a dramatic increase in the H2 S tolerance of NiW and thus, showed much higher activity than NiMo/ASA and NiMo/alumina catalysts. Pt/ASA was found to be more active but its sulfur tolerance was much lower than NiW-based catalysts [1,2]. Navarro et al. [3] reported their study on ASA-based transition metal sulde catalysts, promoted by Pt, Ni, Ru and Pd for HDS activity using DBT. Mo incorporation was responsible for the decrease in the acidity of the catalyst. The promoters enhanced Mo surface exposure and decrease the reduction temperature of MoO3 . Pd was not found to be very effective as a promoter due to its poor dispersion. The HDS activities were found to have the following trend: Pt/ASA PtMo RuMo > PdMo Mo ASA. Fujiwaka et al. [4] reported a study to develop a new sulfur-tolerant noble metal catalyst with signicantly increased catalytic activity for aromatic hydrogenation. The screening tests of the various non-zeolitic noble metal catalysts were carried out with hydrotreated light cycle oil (LCO)/straight-run light gas oil (SRLGO) feed containing 3234 vol.% aromatics and 172474 ppm sulfur at a temperature of

300 C, hydrogen pressure of 4.9 MPa, and LHSV of 1.5 h1 . The Pt-Pd/SiO2 -Al2 O3 catalyst was the most highly active catalyst for aromatic hydrogenation under the conditions applied. The co-existence of Pt with Pd on SiO2 -Al2 O3 remarkably enhanced the catalytic activity, which depended on the Pd/(Pt + Pd) weight ratio and reached a maximum of about 0.7 Pd/(Pt+Pd) weight ratio. Furthermore, the long-term stability test under industrial operating conditions demonstrated the excellent stability of the Pd-Pd/SiO2 -Al2 O3 catalyst. The results of a study involving alumina show that the inhibiting effect of hydrogen sulde on sulfur, nitrogen and aromatics contents is lower at high temperature [5]. A study describing the preparation of a MoO3 /Al2 O3 catalyst revealed that the dispersion of Mo oxide and Mo sulde species increased with the surface area of the support and was directly proportional to the HDS activity of sulded MoO3 /Al2 O3 . It was demonstrated that the formation of crystalline MoO3 was strongly correlated with the Mo segregation on the outer surface of the extrudates [6]. It was suggested that, when a pore volume impregnation or incipient wetness technique is employed, rapid drying at a reduced pressure results in the segregation of Mo oxides on the outer surface of the extrudates, and accordingly formation of crystalline MoO3 . On the other hand, drying under static conditions is favorable for a homogeneous distribution of Mo [7,8]. It was also found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased. The increase in pH (28) of the impregnation solution was found to reduce the dispersion of Mo oxide species. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere [9]. The main objective of this study was to prepare heavy oil hydrocracking catalysts using silica-alumina and zeolite supports, and then to characterize and evaluate their activity and selectivity performance. The sequence of work tasks involved in this study consists of support materials selection, characterization, preparation of extrudates with alumina binder and then impregnation of metal pairs. The nished catalysts were then evaluated for their characteristics and catalytic performance.

M.A. Ali et al. / Applied Catalysis A: General 233 (2002) 7790 Table 1 Properties of supports used for catalysts preparation Number Property Support materials SIRAL 40 (Silica-alumina) 1 2 3 4 5 6 SiO2 /Al2 O3 Surface area BET (m2 /g) Color Pore volume Na/Na2 O F/Fe2 O3 1.2 514 White 0.87 7 ppm as Na2 O 109 ppm as Fe2 O3 USY-zeolite 14.0 671 White 500 ppm as Na2 O -zeolite

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25.0 400 White < 300 ppmw as Na < 500 ppmw as F

2. Experimental 2.1. Selection of catalyst supports and alumina binder Three different materials were selected as catalyst supports based on their acidities and surface areas. These supports were ASA, SIRAL 40 (from Condea GmbH Germany), USY zeolite (from Toso Chemical Company, Japan) and -zeolite (from Sud-Chemie) while alumina-based Cataloid AP-1 (from Catalyst and Chemical Industry, Japan) was used as a binder to prepare extrudates. Cataloid AP-1 comprises 71 wt.% alumina, 11 wt.% acetic acid and 18 wt.% water and it has an average particle size of 54 m. The properties of catalyst supports are given in Table 1. 2.2. Preparation of extrudates The supports selected were rst weighed and then mixed with a weighed amount of AP-1 and formed into 1/32 in. extrudates. This procedure was started with the weighing of the supports, Cataloid AP-1 and water in predetermined quantities and then mixing them together. The mixture was agitated strongly to change it to hard paste. The paste was put into the syringe barrel and pressed to form extrudates which were collected on a lter paper tray. The extrudates were dried in an oven maintained at 120 C for 2 h and then broken into small 34 mm pieces, sieved and calcined in a quartz tube calcination setup provided with air ow. The extrudates were housed between the glass wool in the quartz tube and xed in the heating furnace and connected to an airow of 250 ml/min1 . The temperature was raised to 120 C and maintained for 30 min. Then the temperature was increased to 550 C and

maintained at this temperature for 2 h. Then the heating was stopped, the furnace was opened and the extrudates were allowed to cool to ambient temperature while the air was owing to provide rapid cooling. The extrudates were then removed from the quartz tube and sieved to remove any powder present. Then the extrudates were weighed to record the weight of extrudates formed. 2.3. Metal Impregnation procedure The extrudates were impregnated with metals pairs NiW or NiMo using co-impregnation technique, the metal loading was NiO 4 wt.% and WO3 15 wt.% or MoO3 15 wt.%. Two types of solutions were prepared: one contained Ni and W while the other had Ni and Mo. The solutions were prepared using deionized water. The metal salts used were nickel nitrate hexahydrate [Ni(NO3 )2 6H2 O], ammonium metatungstate pentahydrate [(NH4 )6 W12 O39 5H2 O] and ammonium molybdate tetrahydrate [(NH4 )6 Mo7 O24 4H2 O]. In case of NiMo solution, the ammonium molybdate tetrahydrate was added rst in water and dissolved completely. Then the predetermined quantity of nickel nitrate was added; the mixture was stirred quickly and the solution was used within 12 min before the solution got turbid due to complex formation. The metals were impregnated on a batch of 10 g of extrudates in a wide-mouthed crucible. The solutions were added dropwise till all the extrudates were completely wet. The extrudates were then allowed to adsorb the metals for 2 h. Then the extrudates were placed in an oven maintained at 120 C under a reduced pressure of 410 mmHg pressure for 2 h. The purpose of drying under vacuum was to segregate and bring the Mo ions onto the surface of the catalysts and

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convert them into MoO3 and thus to provide high hydrogenation activity on the surface of the catalyst [8]. At the end of the drying process, the extrudates were placed in a temperature-programmed furnace for calcination. The calcination was conducted under the following heating program: The temperature was raised to 120 C and maintained for 2 h, then the temperature was raised to 550 C at a heating rate of 2 C/min and maintained for 2 h at this temperature. Then the furnace was allowed to cool overnight. The samples were kept in airtight glass bottles for characterization and catalytic evaluation. The weights of the nished catalysts obtained after calcination were in the range 12.613.0 g per batch. 2.4. Characterization of supports and catalysts The acid properties of the supports and catalysts were determined by temperature-programmed desorption of ammonia. The system was a multitask TPD unit (BELL, Japan). About 0.05 g of each powdered sample was placed in a quartz tube reactor and was pretreated to 500 C for 2 h. Ammonia (purity 99.99%) was adsorbed at 100 C (to avoid excessive physical adsorption) for 30 min at 100 Torr. Thermal desorption of ammonia was then conducted at 100 Torr using helium as a carrier gas and raising the temperature up to 600 C at a rate of 10 C/min. The amount of desorbed ammonia was monitored by a Quadruple Mass detector (Massmate 200). For acidity quantication, a pentasil type ZSM-5 zeolite (JRC-Z5-25H) was used as a standard. This zeolite was white in color, having SiO2 /Al2 O3 molar ratio of 25, a BET surface area of 300 m2 /g and containing less than 100 ppm Na. The catalysts were characterized for their surface area and porosity using a nitrogen adsorption method according to ASTM D 3663 using NOVA 1200 from Quantachrome. 2.5. Catalysts performance evaluation in a xed-bed ow reaction system The evaluation of hydrocracking catalysts was carried out under variable operating conditions of temperature and pressure in a xed-bed ow reaction system. The feedstock used for the catalyst evaluation experiments was desulfurized vacuum gas oil (DS-VGO)

obtained from a renery in Japan. Since the DS-VGO was solid at room temperature, it was heated to 50 C to make it a homogenous liquid before use. The ow reactor evaluation of the catalysts was conducted in a packed-bed reaction system having multiple reactors for simultaneous evaluation of ve catalysts. The reaction system was provided with a 10 cm3 tubular reactor, a sand bath heater for reaction temperature and the long glass burettes in the feed tank were attached to the feed pump. The catalysts were presulded in situ before the activity evaluation tests were performed. The hydrocracking reaction conditions selected were as follows: pressure 100 kg/cm2 (1400 psi), hydrogen ow rate of NL/h, hydrogen gas to hydrocarbon ratio of 5900 scfb, operating temperature range from 380 to 410 C, feed rate of 10 ml/h and liquid hour space velocity of 1.0. DS-VGO was utilized as feedstock for the evaluation of the catalysts. Ten millilitre, each of three different catalysts were measured in three 10 ml graduated cylinders with tapping and the weights of the catalysts were recorded. These three catalysts were loaded in three separate reactors with glass wool plugging and aluminum packing rings at both ends of the reactors. These reactors were installed in a sand bath heater. After installation of the reactors to the unit, reactors were pressurized up to 10 Mpa hydrogen pressure for leak test and kept overnight to detect any leak present. The catalysts was then sulded using H2 S in H2 mixture at 400 C for 2 h. After presulding, the temperature was lowered to 200 C and then the H2 S in H2 mixture was replaced by pure hydrogen and the reactors were pressurized up to 10 Mpa. Then, DS-VGO feedstock and hydrogen gas ow rates were set to obtain a space velocity of two and a H2 gas/ hydrocarbon feed ratio of 5900 scfb. After the operation became stabilized, temperature was gradually raised to three reaction temperatures and the conditions were allowed to stabilized. At each reaction temperature, the samples of gas and liquid were collected. Liquid samples were analyzed for simulated distillation and sulfur and nitrogen contents, while the gas samples were analyzed for gaseous components present. At the end of each catalyst run that lasted for 30 h, the run was stopped and spent catalysts were collected. The cracking activity of the catalysts in terms of percent conversion and percent hydrogenation (HDS and HDN) was calculated. The percent conversion was dened as the sum

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of the amount of gas and liquid products produced (gasoline +kerosene +gas oil fraction) while the HDS and HDN activities were calculated by determining the sulfur and nitrogen contents of the feed and reaction products.

Table 2 Properties of DS-VGO feedstock Properties Physical property results Color Appearance Results Greenish dark brown Solid at room temperature 0.890

3. Characterization of DS-VGO feed and hydrocracking reaction products 3.1. Elemental analysis The DS-VGO feed and hydrocracking reaction products were analyzed for their sulfur and nitrogen contents using an elemental analyzer Model ANTEK 7000 provided with an ANTEK 735 Syringe drive. The lower detection limit of this analyzer was 10 ppm for total sulfur and nitrogen content. 3.2. Boiling range distribution

Density (15 C, g/cm3)

SIMDIST distillation fractions (temperature, C) Kerosene (150250 C) (%) 0.0 Gas oil (250343 C) (%) 8.9 Vacuum gas oil (343520 C) (%) 84.7 6.4 Vacuum residue (> 520 C) (%) Elemental analysis results Sulfur content (wt.%) Nitrogen content (wt.%) 0.289 0.028

4. Results and discussion 4.1. Characterization The boiling range distribution of DS-VGO feedstock and hydrocracking reaction products was determined by a simulated distillation analyzer using the ASTM method D 2887. The system consisted of a Shimadzu gas chromatograph equipped with an automatic sampler, a ame ionization detector (FID) and a packed column (3 1000 mm) silicone OV-1 Chromosorb W 60/80 AW-DMCS (Shimadzu). The gas chromatograph was calibrated by analyzing a mixture of normal parafns with known boiling points. 3.3. Gas composition analysis The compositions of the gas products were determined by gas chromatography. The system consisted of a Shimadzu gas chromatograph equipped with a sampling loop and two columns (from Shimadzu): Sunpak-S for H2 S separation from hydrocarbon gases and Porapak-Q for hydrocarbon gases separation. The detection of the separated components was performed using a ame ionization detector FID for hydrocarbon gases and a thermal conductivity detector for H2 S determination. The hydrogen contents of the gas samples were determined by differences. The gas chromatograph was calibrated by analyzing a mixture of hydrocarbon gases and H2 S. 4.1.1. Feedstock characterization The properties of DS-VGO feedstock are given in Table 2. 4.2. Catalysts characterization 4.2.1. Surface area and porosity The compositions of the prepared catalysts are given in Table 3 along with their surface characteristics and porosity in terms of BET surface area, pore volume and average pore radius. The surface area and pore radius and pore volume values obtained are of the catalysts containing zeolite, silica-alumina and binder and thus represent the properties of the mixed supports. The catalysts loaded with Mo showed lower surface area compared to those having W loadings. Similarly, catalysts prepared with -zeolite showed lower surface area as compared to those having USY zeolites. 4.2.2. Acidity by ammonia TPD method The supports were characterized for their acidities using ammoniaTPD method. The results are given in Table 4 and the TPD prole is given in Fig. 1. It was found that -zeolite possesses higher

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Table 3 Composition of the prepared catalysts and surface characteristics Catalyst designation (composition) Cat-1 (USY-ASA/NiMo) Composition of the catalysts 40 wt.% USY-zeolite, 30 wt.% SIRAL 40 and 30 wt.% AP-1 having 4 wt.% NiO and 15 wt.% MoO3 40 wt.% USY-zeolite, 30 wt.% SIRAL 40 and 30 wt.% AP-1 having 4 wt.% NiO and 15 wt.% WO3 40 wt.% -zeolite, 30 wt.% SIRAL 40 and 30 wt.% AP-1 having 4 wt.% NiO and 15 wt.% MoO3 40 wt.% -zeolite, 30 wt.% SIRAL 40 and 30 wt.% AP-1 having 4 wt.% NiO and 15 wt.% WO3 40 wt.% -zeolite and 60 wt.% AP-1 having 4 wt.% NiO and 15 wt.% WO3 Surface area (m2 /g) 284.8 Pore volume (cm3 /g) 0.37 Average pore radius () 26.3

Cat-2 (USY-ASA/NiW) 364.0 0.45 24.8

Cat-3 ( -ASA/NiMo)

266.1

0.42

31.6

Cat-4 ( -ASA/NiW)

310.5

0.44

28.5

Cat-5 ( /NiW)

254.9

0.34

26.7

acidity as compared to the acidities of USY and silica-alumina supports, although the SiO2 /Al2 O3 ratio of -zeolite is 25, whereas USY-zeolite contains high aluminum. The reason may be because the USY zeolite is ultrastable or steamed and thus, possesses a considerable amount of nonframework aluminum which does not exhibit any acidity by ammonia method. 4.3. Catalysts performance evaluation The hydrocracking products of DS-VGO using ve catalysts were analyzed for boiling range distribution, and sulfur and nitrogen contents, and were evaluated for composition of products, conversion of different fractions and hydrogenation activity. The results indicate a marked degree of conversion of DS-VGO feed into gas, naphtha, kerosene, and gas oil. The converTable 4 Acidity (mmol/g) of catalyst support determined by ammonia TPD method Support type USY-zeolite -zeolite SIRAL 40 ZSM-5 (reference) Weak acidity Strong acidity Total acidity 0.040 0.082 ND 0.287 0.173 0.564 ND 0.703 0.213 0.646 0.298 0.990

sion of the feed was calculated as the sum of the percent concentration of product gas, naphtha, kerosene, and gas oil produced. 4.4. Cracking activity The cracking activity of all catalysts was found to increase with rise in temperature. The amounts of gas, naphtha, kerosene and gas oil increased with the temperature for all catalysts, while the amounts of VGO and VR fractions decreased. At 380 C reaction temperature and 1114 h on stream, all ve catalysts were evaluated. The cracking activities of USY-ASA-based catalysts were found lower than those of -ASA and -zeolite-based catalysts (Table 5). ASA stands for amorphous silica-alumina, SIRAL 40. This is attributed to the high acidity of -zeolite. The cracking activity of USY-ASA/NiMo catalyst was slightly higher than that of the USY-ASA/NiW catalyst in the production of gas oil fraction. In the case of -ASA-based catalysts, the cracking activity of NiMo-based catalyst was higher than that of NiW loaded catalyst for gas and naphtha production. The cracking activity of /NiW catalyst was lower than those of the -ASA/NiW and -ASA/NiMo catalysts (Fig. 2). The -zeolite-based catalysts produced higher amounts of naphtha and lower amounts of kerosene and gas oil fractions while USY-based catalysts produced higher amounts of

ND: weak and strong acidity peaks could not be differentiated.

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Fig. 1. Ammonia TPD prole of supports used for catalyst preparation.

gas oil and lower amounts of kerosene and naphtha (Fig. 3). At 395 C temperature and 1822 h on stream, the cracking activity of USY-ASA/NiMo was slightly

higher than that of USY-ASA/NiW catalyst in the production of naphtha, kerosene and gas oil fractions (Table 6). This is similar to the trend observed at 380 C. In the case of -ASA-based catalysts, the

Table 5 Results of catalysts evaluation at 380 C temperatures in xed-bed ow reaction system Catalyst type (supports/metal loaded) Reaction temperature (380 C); time on stream (1114 h) USY ASA/NiMo LHSV at Material balance (%) Composition of products (%) Gas Naphtha(150 C <) Kero(150250 C) GO (250343 C) VGO (343520 C) VR (> 520 C) Conversion (%) GO conversion VGO conversion VR conversion Total conversion (250 C <) Hydrogenation activity (%) HDS HDN 15 C 0.97 100.4 0.4 1.9 3.7 15.3 75.5 3.2 13.7 10.9 50.2 12.4 88.8 92.9 USY + ASA/NiW 1.00 101.2 0.4 2.3 4.0 13.8 75.8 3.7 12.7 10.5 42.4 11.6 91.5 93.2 + ASA/NiMo 0.99 102.3 8.7 23.4 12.0 9.5 43.2 3.2 49.1 49.0 50.1 44.7 93.9 94.4 + ASA/NiW 1.04 102.1 5.3 20.6 13.9 11.9 44.9 3.4 47.0 47.0 46.7 42.8 94.9 94.6 /NiW 1.07 106.8 5.3 20.2 12.9 11.3 47.0 3.4 44.7 44.6 46.7 40.7 95.3 91.5

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Fig. 2. Conversion of the DS-VGO feed at 380 C temperature using different catalysts.

Fig. 3. Distribution of product components at 380 C temperature using different catalysts.

M.A. Ali et al. / Applied Catalysis A: General 233 (2002) 7790 Table 6 Results of catalysts evaluation at 395 C temperatures in xed-bed ow reaction system Catalyst type (supports/metal loaded) Reaction temperature (395 C); time on stream (1822 h) USY ASA/NiMo LHSV at Material balance (%) Composition of products (%) Gas Naphtha(150 C <) Kero(150250 C) GO (250343 C) VGO (343520 C) VR (> 520 C) Conversion (%) GO conversion VGO conversion VR conversion Total conversion (> 250 C) Hydrogenation activity (%) HDS HDN 15 C 0.96 100.5 0.9 4.7 8.3 16.5 66.6 3.0 23.7 21.4 53.6 21.6 93.6 >96.0 USY + ASA/NiW 1.05 91.4 0.8 4.1 7.2 16.0 68.6 3.4 21.0 19.0 47.3 19.1 93.9 95.7 + ASA/NiMo 0.98 96.6 9.4 34.1 15.5 9.3 30.2 1.5 65.2 64.4 75.9 59.4 97.2 >96.0 + ASA/NiW 1.04 94.8 8.2 40.4 17.7 8.4 23.7 1.7 72.2 72.0 74.2 65.8 97.7 >96.0

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/NiW 0.88 92.5 8.8 45.5 17.0 6.6 21.1 1.0 75.8 75.1 84.3 69.0 98.5 >96.0

cracking activity of NiW-based catalyst was higher for NiW-loaded catalyst as compared to NiMo-loaded catalyst. The cracking activity of /NiW catalyst was higher than those of the -ASA-based catalysts (Fig. 4). In terms of product composition, higher activity resulted in the higher amounts of naphtha and kerosene (Fig. 5). At 410 C and 2830 h on stream, the cracking activity of -ASA/NiW catalyst was found highest among all the catalysts followed by /NiW and -ASA/NiMo catalyst (Tables 7 and 8). The other two catalysts USY-ASA/NiW and USY-ASA/NiMo showed lower activity. Thus the -zeolite-based catalysts performed much better than the USY-based catalyst (Fig. 6). In terms of product distribution, the USY-based catalysts produced lower amount of gas as compared to -based catalysts and it was directly proportional to their overall activities. The USY-ASA/NiW catalyst showed slightly higher amounts of naphtha, kerosene and gas oil as compared to USY-ASA/NiMo catalyst. In the case of -ASA/NiMo catalyst, the naphtha produced was less but amounts of gas, kerosene and gas oil were higher than for -ASA/NiW and /NiW catalysts (Fig. 7). Among the gas product components, the isobutene was found to be in highest quantity followed by propane and isopen-

tane. The NiW-loaded catalysts produced lower gas amounts compared to the NiMo-loaded catalysts. Generally, for all the catalysts, the gas production was found directly proportional to their cracking activities. 4.5. HDS activity The HDS and HDN activities are shown in Fig. 8. At 380 C, the HDS activity of USY-ASA/NiW was higher than that of USY-ASA/NiMo catalyst. In the case of -ASA-based catalysts, the HDS activity of NiW loaded catalyst was slightly better than that of NiMo-loaded catalyst. At 395 C, the HDS activity of USY-ASA/NiW was similar to that of USY-ASA/NiMo catalyst. Higher HDS activities (>97%) were obtained by -ASA-NiW, -ASA/NiMo and /Ni-W catalysts as compared to those obtained by USY-ASA/NiMo and USY-ASA/NiW catalysts (94%). This trend of higher HDS activity was also observed in reaction products obtained at 410 C. At 380 C, the HDN activities of USY/ASA/NiW and USY/ASA/NiMo catalysts were lower than those of -ASA catalysts. At temperatures of 395 and 410 C, the HDN activities of all the catalysts were greater than 96%.

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Fig. 4. Conversion of the DS-VGO feed at 395 C temperature using different catalysts.

Fig. 5. Distribution of product components at 395 C temperature using different catalysts.