Applied Catalysis A: General 260 (2004) 137151

A series of NiMo/Al2 O3 catalysts containing boron and phosphorus Part I. Synthesis and characterization
D. Ferdous a , A.K. Dalai a, , J. Adjaye b
a

Catalysis and Chemical Reactor Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Canada SK S7N 5C9 b Syncrude Canada Ltd., Edmonton Research Center, Canada Received 13 March 2003; received in revised form 9 October 2003; accepted 9 October 2003

Abstract In this work, a series of nickelmolybdenum, nickelmolybdenumboron and one nickelmolybdenumphosphorus catalysts were prepared by incipient wetness impregnation method. Calcination temperature, nickel, molybdenum and boron concentrations in -Al2 O3 were varied from 450 to 600 C, 1.8 to 3.1 wt.%, 10.6 to 13.2 wt.% and 0.5 to 1.7 wt.%, respectively. Nickelmolybdenumphosphorus catalyst was prepared using 2.7 wt.% phosphorus. All catalysts were thoroughly characterized. The catalyst containing 10.6 wt.% Mo and 2.4 wt.% Ni in -Al2 O3 gave maximum BET area of 211 m2 /g. In these catalysts, the molybdenum oxides were present predominantly as polymolybdate and tetrahedral form. Addition of boron to NiMo/Al2 O3 caused an increase in weak acid centers, whereas phosphorus caused the formation of acid centers with intermediate strength. Also, addition of boron caused the formation of crystalline B2 O3 and MoO3 on the catalyst surface, evident from both XRD and SEM analyses. Whereas addition of phosphorus caused the formation of irregular particle size and agglomeration on the catalyst surface, evident from SEM-EDS analysis. New Lewis and Brnsted acid sites on the catalyst surface were observed from FTIR analysis because of the addition of boron and phosphorus to NiMo/Al2 O3 . 2003 Elsevier B.V. All rights reserved.
Keywords: NiMo/Al2 O3 catalysts; Boron; Phosphorus; TPR; TPD; XRD; NMR; FTIR; HDN; HDS

1. Introduction Oil sand bitumen and the bitumen derived gas oil contain high levels of nitrogen and sulfur compounds. Thus, the products such as heavy gas oil obtained from the processing of bitumen also contain very high levels of nitrogen. Catalytic hydrodenitrogenation (HDN) is the only process used commercially for reducing the level of nitrogen content in those types of feed stocks. Because of high nitrogen content hydrodenitrogenation (HDN) of this heavy gas oil is more difcult and less effective with conventional NiMo/Al2 O3 catalyst. In the past some attempts have been made to modify NiMo/Al2 O3 catalyst using boron to improve hydrodenitrigenation (HDN) of model nitrogen compounds. Borate ion incorporated on alumina forms a system exhibiting acidic
Corresponding author. Tel.: +1-306-966-4771; fax: +1-306-966-4777. E-mail address: dalai@engr.usask.ca (A.K. Dalai). 0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2003.10.010

properties. Peil et al. [1] and Wang and Chen [2] showed that incorporation of borate ions increased alumina acidity. Moreover, borate ions brought about an increase in the activity of CoMo/Al2 O3 and NiMo/Al2 O3 catalysts in the reaction of HDS [3,4]. Lulic [5] investigated the performance of NiMo/Al2 O3 B2 O3 catalyst on the HDN activity and concluded that the catalysts containing boron are more active than commercial HDN catalyst. DeCanio and Weissman [6] studied the characterization and activity of boron (0.31.8 wt.%) modied commercial NiMo/Al2 O3 catalyst. At higher boron loadings of over 1.8 wt.% boron, poor catalytic performance was observed due to the presence of bulk borate phase. Lewandowski and Sarbak [7] studied the effect of boron addition on texture and structure of NiMo/Al2 O3 catalysts. They found that addition of boron did not change the pore volume signicantly; however, it increased the pore radius to 20, 25, 30 and 40 in comparison with the unmodied catalyst. Lewandowski and Sarbak [8] studied the HDS and HDN activities of boron modied NiMo/Al2 O3 catalyst using quinoline, carbazole and coal liquid. The support with

138

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

borate ions increased the acidity of NiMo catalyst; in particular, the amount of acid centers of intermediate strength. The HDN activity of the catalyst containing 9.1 and 11.7 wt.% boron was considerably higher than that of NiMo catalyst. They concluded that the HDN of carbazole indeed depends on the number of acid centers present on the catalyst surface. On the other hand, in the case of quinoline, the acid centers also play a certain role; however reaction may proceed on centers of weak strength. They also concluded that a support modication with borate ions led to a decrease in deactivation of the NiMo catalyst in the HDN of coal liquid. The presence of small amounts of phosphorus in sulded NiMo/Al2 O3 catalyst has been shown to have a positive effect on both their HDN and HDS activities. In addition, these catalysts are less susceptible to coking [9]. Various explanations are proposed for this improvement. It has been reported that phosphorus enhances the solubility of the molybdate by the formation of phosphomolybdate complexes, which make the catalyst preparation easier and may lead to a different dispersion of the Mo and Co/Ni. Also, addition of phosphorus causes the formation of easily reducible and sulded forms, such as multilayered molybdate, crystalline Al2 (MoO4 )3 and MoO3 on the catalyst surface [911]. On the other hand, phosphorus causes interactions of metal atoms with alumina support surface in case of sulded cobalt and nickel [12]. However, Iwamoto and Grimblot [13] reported that phosphorus modies the textural characteristic and acidity of the catalysts. From work on the unpromoted MoP/Al2 O3 catalyst, they have shown that the thiophene HDS activity was not promoted by phosphorus loading, while large amount of phosphorus decreased the catalytic performances, probably by formation of bulk MoO3 in oxide precursor. Eijsbouts et al. [14] found benecial effects of phosphorus in studies of quinoline HDN. They have suggested that, phosphorus may play a direct role in CN bond cleavage. On the other hand, Lewis et al. [11] and Eijsbouts et al. [14] did not nd any positive effect of phosphorus during hydrodesulfurization of thiophene. This discrepancy was explained by assuming that the HDN and HDS reactions take place on different catalytic sites and phosphorus has different inuence on them. Jian et al. [15] found no effects in the HDN of piperidine and pyridine over NiMo/Al2 O3 catalyst. But in the presence of phosphorus the HDN activity decreased as the phosphorus content in the catalyst increased. They have concluded that phosphorus has a negative effect on the CN bond cleavage in piperidine, as well as on the subsequent hydrogenation of the C5 alkene intermediates. In the past, most of the research has been performed by modifying the support with boron. However, little information is available on the modication of NiMo/Al2 O3 itself with boron. Although a number of researchers and commercial operations use P modied NiMo/Al2 O3 catalysts, in the open literature, most studies have been conducted using HDN of model compounds and for short run lengths. Information on performance of B and P on the hydroprocessing of actual feed is scarce. The correlation between catalyst

properties with the HDN activity is also missing especially when the feed is gas oils derived from the oil sands. Consequently, in the present work, a series of NiMo/Al2 O3 catalyst was prepared using different concentrations of B and P, and thoroughly characterized (Part I). The impact of B and P on the catalytic properties as well as on HDN and HDS performances of heavy gas oil derived from oil sands bitumen were also investigated (the results of which constitutes Part II of this work).

2. Experimental 2.1. Catalyst preparation A series of NiMo/Al2 O3 was prepared using incipient wetness coimpregnation method using extruded -Al2 O3 (1.4 mm of diameter) obtained from Sud Chemical India Ltd., New Delhi. In this method an ammoniacal solution (28 wt.% concentrated NH3 ) was prepared at a pH of 9.5 using required amount of ammonium heptamolybdate [(NH4 )6 Mo7 O24 4H2 O] and nickel nitrate [Ni(NO3 )2 6H2 O]. The solution was heated at 70 C until it produced a clear solution, and was impregnated with support (dried at 120 C for overnight). The impregnated support was dried for 12 h at 120 C. The catalyst was then calcined at different temperatures (450600 C) for 4 h. Catalysts were prepared at different Ni (1.83.1 wt.%) and Mo (10.613.2 wt.%) concentrations. NiMoB/Al2 O3 catalysts were prepared by impregnating appropriate solution of boric acid on to a NiMo/Al2 O3 catalyst. The pH of the solution was maintained at 7. The resulting modied catalysts were then dried at 120 C for 12 h. Finally the catalysts were calcined at 500 C for 4 h. NiMoP/Al2 O3 catalyst was prepared using incipient wetness coimpregnation method. In this method, a solution containing required amount of ammonium heptamolybdate [(NH4 )6 Mo7 O24 4H2 O], nickel nitrate [Ni(NO3 )2 6H2 O] and phosphoric acid (H3 PO4 ) in water was impregnated onto an Al2 O3 support. The pH of the solution was maintained 3.5 using 28 wt.% concentrated NH3 solution. Impregnation of the support was followed by drying for 12 h at 120 C and calcined at 500 C for 4 h. 2.2. Catalyst characterization Catalyst characterization was carried out to identify the properties of the catalysts that are responsible for the catalyst activity. Different characterization techniques used in this study are described below. 2.2.1. Elemental analysis The analysis of the elemental composition of Ni, Mo, B and P in the calcined catalyst was performed using inductivity coupled plasma-mass spectrometer (ICP-MS). The procedure is described by Ferdous [16].

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

139

2.2.2. BET surface area, pore volume and pore size measurement BET surface area, pore volume and pore size measurements of the calcined catalysts (0.1 g) were performed using a Micromeritics adsorption equipment (Model ASAP 2000, manufactured by Micromeritics Instruments Inc., Norcross, GA, USA) at 78 K using liquid N2 . Before analysis, catalyst sample was evacuated at 200 C for 4 h in a vacuum of 5 104 atm to remove all adsorbed moisture from the catalyst surface and pores. 2.2.3. Temperature programmed reduction The temperature programmed reduction (TPR) analysis of the catalyst (0.03 g) was performed using Quantachrome equipment (Model ChemBET 3000, Manufactured by Quantachrome Corporation, FL, USA). The sample U tube was placed in an electric furnace and heated from 22 to 1050 C at 20 C/min at 1 atm in a reducing gas of 3 mol% H2 in N2 (obtained from Praxiar, Mississauga, Ont., Canada) with a ow rate of 30 ml/min. H2 consumption during the TPR experiments was measured with a thermal conductivity detector (TCD). The TPR plots were logged using an on-line data acquisition system. 2.2.4. Temperature programmed desorption The temperature programmed desorption (TPD) of ammonia was performed using Quantachrome equipment (Model ChemBET 3000, Manufactured by Quantachrome Corporation, FL, USA) for the measurement of the acidic properties of catalysts. For TPD analysis, 0.1 g catalyst sample was placed in an adsorption vessel (U-shaped), heated with a ow of 0.1% NH3 in N2 at the ow rate of 20 ml/min and at heating rate of 10 C/min up to 400 C and kept at this temperature for 1 h. Then it was cooled to room temperature using this gas mixture at the same ow rate. Finally, the TPD was run from room temperature to 1050 C at heating rate of 10 C/min with He ow at 20 ml/min. The amount of NH3 desorbed was measured using a TCD. 2.2.5. X-ray diffraction Powder X-ray diffraction (XRD) studies were performed on the calcined sample in order to identify the crystalline species present. XRD analysis was performed using Rigaku diffractometer (Rigaku, Tokyo, Japan) using Cu K radiation ltered by a graphic monochromator at a setting of 40 kV and 130 mA. The powdered catalyst samples were smeared on glass slide with methanol and dried at room temperature. The X-ray diffraction analysis was carried out in the scanning angle (2 ) range of 360 at scanning speed of 5 /min. 2.2.6. Scanning electron microscopyenergy dispersion spectroscopy Scanning electron microscopy (SEM) analysis was performed on NiMo/Al2 O3 catalysts using Hitachi S-2700 with Princeton Gamma-Tech Prism EDS Detector at Syncrude

Canada Ltd. For doing this analysis, a few pellets of the catalyst samples were attached onto an aluminum stub using epoxy as the adhesive. Before doing the analysis the samples were coated with carbon by vacuum evaporation to reduce charging and improve the secondary electron signals for imaging. Analysis was done for the surface and also for the radial direction of the catalyst samples at the magnication of 12 000. In addition, energy dispersion spectroscopy (EDS) was also used to obtain the elemental analysis for selected particles. 2.2.7. Nuclear magnetic resonance NMR analysis of all calcined catalysts was performed using an Advance DRX NMR spectrometer, manufactured by Bruker Analytik GmbH. The study looks at the different hydroxyl structures present on the catalyst surface. For this analysis 1 H (proton) nucleus (360.13 MHz) was observed. Approximately 0.5 g of sample was packed in the rotor. The rotor was placed in the probe and spinning started to a speed of 5 kHz. The sample sits at an angle of 54.7 , which is referred to as magic angel spinning (MAS). The data was collected for 2.2 min and then transformed to produce the spectra. 2.2.8. Fourier transform infrared spectroscopy Fourier transform infrared (FTIR) analysis of all catalysts was performed using an FTIR spectrometer attached to a photo acoustic spectroscopy (PAS) cell. Before doing analysis all samples were powdered and dried in an oven at 400 C for 3 h, cooled in the desiccator until it reached about 50 C whereupon it was transferred into a sample cup stored in the desiccator. The loaded cup was inserted into the PAS measurement chamber and the atmosphere control valve rotated to the open purge position to allow helium gas to ow over the sample. Then the rear lever was rotated to the closed purge position and the sample allowed to cool to room temperature, in the sealed cell, under helium. All spectra were recorded after 512 scans at a resolution of 8 cm1 in order to achieve desired signal to noise ratio.

3. Results and discussion 3.1. Catalyst characterization 3.1.1. Elemental analysis Table 1 shows the elemental analysis of the different catalyst formulations. It is observed that for all catalysts the measured concentrations are comparatively lower than those of targeted ones particularly in case of Mo. For example, for the catalyst with the targeted Ni and Mo concentrations of 4 and 14 wt.%, the actual concentrations were 3.1 and 11.1 wt.%, respectively. Part of this discrepancy is due to the inherent nature of these compounds to form considerable metal vacancies, depending on the preparation or heat treatment conditions [17]. Also, the signicant difference in

140

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

Table 1 Summary of ICP results of different NiMo/Al2 O3 , NiMoB/Al2 O3 , and NiMoP/Al2 O3 catalysts calcined for 4 h Catalyst Calcination temperature ( C) 450 500 600 500 500 500 500 500 500 500 500 500 500 500 Targeted (wt.%) Ni 3 3 3 2 3 4 3 3 3 3 3 3 3 3 Mo 14 14 14 14 14 14 12 14 14 14 14 14 14 14 B 0 0 0 0 0 0 0 0 0.6 1.2 1.3 1.4 2.0 0 P 0 0 0 0 0 0 0 0 0 0 0 0 0 3 Measured (wt.%) Ni 2.7 2.9 3.0 1.8 2.9 3.1 2.4 2.9 2.6 2.6 2.8 2.5 2.2 3.1 Mo 12.2 13.2 13.2 12.5 13.2 11.1 10.6 13.2 11.7 11.8 9.1 11.8 10.2 12.5 B 0 0 0 0 0 0 0 0 0.53 1.1 1.2 1.3 1.7 0 P 0 0 0 0 0 0 0 0 0 0 0 0 0 2.7

A B C D B E F B G H I J K L

expected and targeted Mo concentrations could be due to the hygroscopic nature of the Mo precursor (ammonium heptamolybdate) thus preventing complete impregnation of Mo from the solution to the support. 3.1.2. BET surface area, pore volume, and pore size measurement The BET surface area, pore volume and pore size of different catalysts are given in Table 2. From this table, it is observed that the surface area, pore volume, and pore diameter of the support decreased with the incorporation of Ni, Mo, B and P in -Al2 O3 , due to: (a) the pore blocking of alumina with impregnated material [7], and (b) the partial solubility of alumina in acid and alkaline media [18]. It is also seen that the increase in calcination temperature caused

an increase in surface area of the catalyst. For example, it increased from 183 to 201 m2 /g with calcination temperature from 450 to 600 C (see Table 2 for catalysts AC). On the other hand Brito and Laine [19] reported no significant change in surface area but slight increase in the pore volume with the increase in calcination temperature from 400 to 500 C. This is probably due to migration of Ni and Mo metal from pore to surface, with the increase in calcination temperature. The surface area increased from 186 to 197 wt.% with the increase in Ni concentration from 1.8 to 3.1 wt.% (Table 2) (catalysts B, D and E). These results are in agreement with those results reported by Brito and Laine [19]. However, an increase in Mo concentration from 10.6 to 13.2 wt.% (catalysts B and F) caused a decrease in surface area from 211 to 193 m2 /g. It is seen from Table 2 that the surface area (192195 m2 /g) did not change signicantly with the addition of 0.51.2 wt.% B to the NiMo/Al2 O3 catalyst (catalysts GI) but it decreased signicantly with the increase in B to 1.7 wt.% (catalysts J and K). This decrease is due to the blockage of pores and the formation of bulk and crystalline B2 O3 at higher boron loading. Lewandowski and Sarbak [7] also reported a decrease in surface area of NiMoB/Al2 O3 catalyst from 163 to 123 m2 /g with an increase in boron concentration from 2.8 to 11.7 wt.%. The surface area of the catalyst did not change with the addition of P to this catalyst. In contrast, Jian and Prins [20] reported decrease in surface area from 212 to 174 m2 /g with the addition of 2 wt.% P to NiMo/Al2 O3 . The pore volume and pore diameter of all catalysts varied between 0.42 and 0.52 cm3 /g, and 91 and 107 , respectively. 3.1.3. Temperature programmed reduction Temperature programmed reduction (TPR) analysis was performed to determine the nature of different oxide species present on the calcined catalyst surface as well as to study

Table 2 BET surface area, pore volume and pore diameter of different NiMo/Al2 O3 , NiMoB/Al2 O3 and NiMoP/Al2 O3 catalysts calcined for 4 h Ni Support 2.7 2.9 3.0 1.8 2.9 3.1 2.4 2.9 2.6 2.6 2.8 2.5 2.2 3.1 Mo (wt.%) 12.2 13.2 13.2 12.5 13.2 11.1 10.6 13.2 11.7 11.8 9.1 11.8 10.2 12.5 B 0.5 1.1 1.2 1.3 1.7 P 2.7 Calcination temperature ( C) 450 500 600 500 500 500 500 500 500 500 500 500 500 500 BET (m2 /g) 235 183 193 201 186 193 197 211 193 195 194 192 185 164 194 Pore volume (cm3 /g) 0.657 0.452 0.487 0.479 0.44 0.487 0.469 0.482 0.487 0.522 0.444 0.459 0.474 0.422 0.43 Pore diameter () 112 99 101 95 95 101 95 91 101 107 92 96 103 103 96

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

141

the reducibility of the catalyst. TPR has been shown to be a sensitive technique for studying reducibility [21] and has been applied successfully for the characterization of CoMo/Al2 O3 [22], NiO/Al2 O3 [23], MoO3 /Al2 O3 [23,24], and NiMo/Al2 O3 [23].

The TPR proles of different NiMo/Al2 O3 catalysts and -Al2 O3 support are given in Fig. 1. Fig. 1a for NiMo/Al2 O3 shows that the lower temperature peak, which is referred to as MoI , shifts from 520 to 490 C, and the higher temperature peak, which is referred to MoII , shifts from 915 to 900 C,

Fig. 1. TPR proles of different NiMo/Al2 O3 catalysts. Effects of: (a) calcination temperature, (b) Ni concentration, (c) Mo concentration, (d) B concentration, and (e) P concentration.

142

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

with the increase in calcination temperature from 450 to 600 C. The peak at 520 C is probably the result of the partial reduction of well-dispersed polymolybdate-like species, i.e. Mo6+ Mo4+ . The peak at 775 C (see Fig. 1a) is because of the reduction of Ni [19]. Its intensity decreased signicantly with the increase in calcination temperature from 450 to 600 C. Brito and Laine [19] reported that at the calcination temperature <600 C, all Ni reduced under the Nii band. The reducibility of Ni depends upon the calcination temperature of the catalyst. It was reported that in NiMo/Al2 O3 catalyst, most of the Ni reduced simultaneously with Mo under the low temperature peak [25]. But at higher calcination temperatures >600 C, essentially all the nickel present reduces with MoII [19]. In contrast, Park et al. [23] reported that the peak at 775 C is probably because of the further reduction of polymolybdate, which exerts a stronger interaction with the support. The peak at higher temperature (915 C) represents complete reduction of polymolybdate plus the reduction of the tetrahedrally coordinated molybdate group i.e. Mo6+ Mo4+ and Mo4+ Mo0+ [23]. Fig. 1a also shows that increase in calcination temperature caused a decrease in peak intensity at 520 C, probably because of Mo loss at the higher calcination temperature [26]. However, hydrogen consumption for these catalysts did not change signicantly with the increase in calcination temperature from 450 to 600 C, which remained at 0.2 l/g of catalyst for all calcination temperatures. The lower temperature peak shifts from 520 to 490 C and peak intensity decreased with increase in Ni concentration from 1.8 to 3.1 wt.% (catalysts B, D and E) but the higher temperature peak did not shift (Fig. 1b). The hydrogen consumption for these catalysts decreased from 0.3 to 0.2 l/g of catalyst with the increase in Ni concentrations from 1.8 to 3.1 wt.%. This may be due to the interaction between Ni and Mo is suggested by Dufresne et al. [27], producing NiMoO phase, which is the precursor of the NiMoS, known as the active site for HDN reaction. A possible role of Ni in enhancing Mo reducibility could be to facilitate hydrogen activation (i.e. decomposition of H2 to atomic hydrogen and migration of polymolybdates e.g. by spill over) [19]. Higher Mo concentration did not change the reduction temperature of the lower temperature peak but decreased the reduction temperature for higher temperature peak slightly from 920 to 915 C (Fig. 1c). No signicant change in total hydrogen consumption (0.2 l/g of catalyst) was observed for these catalysts. The effects of B concentration on TPR prole are given in Fig. 1d, which shows that the addition of B to NiMo/Al2 O3 catalyst (catalysts GK) decreases the reducibility of the catalyst. The reduction temperature of polymolybdate increased from 520 to 605 C with increase in boron concentration from 0 to 1.7 wt.%. Increase in boron concentration also changed the molybdenum oxide structure and caused the formation of less-reducible molybdenum borate. This is conrmed by DeCanio and Weissman [6] using FTIR techniques by NO adsorption that addition of B up to 0.3 wt.%

to NiMo/Al2 O3 catalyst changes molybdenum oxide structure, rendering it more susceptible to reduction. However, by adding B from 0.3 to 1.8 wt.%, decreased the intensity of the NiMo band which indicates that some molybdenum converts to a less easily reducible form such as molybdenum borate. This study conrms the decrease in reducibility of B (0.61.7 wt.%) containing catalysts. The hydrogen consumption for these catalysts increased from 0.2 to 0.5 l/g of catalyst with the increase in B concentration from 0 to 1.7 wt.%. This indicates that addition of B to NiMo/Al2 O3 catalyst caused the migration of higher amounts of Ni and Mo oxides to the catalyst surface. The reduction temperature of polymolybdate and tetramolybdate increased from 520 to 550 C and 920 to 1000 C with the addition of 2.7 wt.% phosphorus to NiMo/Al2 O3 catalyst (see Fig. 1e). The reducibility of the catalyst decreased probably because of the strong interaction of Ni with aluminum phase, and because of the formation of AlPO4 at the support surface [12]. The hydrogen consumption increased from 0.2 to 0.4 l/g of catalyst with the incorporation of 2.7 wt.% P to NiMo/Al2 O3 catalyst. 3.1.4. Temperature programmed desorption Temperature programmed desorption (TPD) of adsorbed ammonia was used to measure the acidic properties of the catalyst. NH3 can be absorbed on the catalyst surface physically and chemically. The physically absorbed NH3 is desorbed at lower temperature whereas chemically absorbed NH3 is desorbed at higher temperature. From the literature, it is observed that there are three ranges of temperature for the desorption of ammonia, namely, 20200, 200350 and 350550 C, which correspond to weak, intermediate, and strong acid centers, respectively [8]. On the other hand, the desorption peak intensity and area measures the number of acid sites, i.e. if the peak intensity and area are high, the number of acid sites is more and vice versa [28]. The proles in Fig. 2 show the acid center for support (Al2 O3 ) as well as for different NiMo/Al2 O3 catalysts calcined at different temperatures and those containing different concentrations of Ni, Mo, B, and P. From this gure, two peaks from 100 to 400 C and 500 to 1000 C for the desorption of NH3 are observed, corresponding to weakintermediate and strong acid centers. The gure shows that the intermediate acid strength increased and the strength of strong acid centers decreased by impregnation of support with molybdenum, nickel, boron, and phosphorus ions, which are evident from the peak intensity and area. The effect of calcination temperature on TPD prole shows that increase in calcination temperature from 450 to 600 C caused an increase in intermediate acid centers but a decrease in strong acid centers (Fig. 2a for catalysts AC). Fig. 2b shows that the increase in Ni concentration caused a decrease in number of acid sites as well as in intermediate acid strength. However, the number of strong acid sites, and those with intermediate and higher strength of support increased with increase in Ni concentration. The increase

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

143

Fig. 2. TPD prole of different NiMo/Al2 O3 catalysts. Effects of: (a) calcination temperature, (b) Ni concentration, (c) Mo concentration, (d) B concentration, and (e) P concentration.

in Mo concentration from 10.6 to 13.2 wt.% caused an increase in number of intermediate and strong acid centers (see Fig. 2c). Increase in boron loading from 0.5 to 1.3 wt.% (catalysts GJ) caused the formation of intermediate acid centers,

whereas 1.7 wt.% boron (catalyst K) concentration caused the formation of weak acid centers as observed from their desorption peak temperature (Fig. 2d). However, addition of phosphorus to NiMo/Al2 O3 catalyst (catalyst L) caused the formation of intermediate acid centers (Fig. 2e).

144

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

3.1.5. Scanning electron microscopyenergy dispersion spectroscopy Scanning electron micrographs are used to study the surface morphology of the fresh catalysts whereas EDS is used to quantify the elemental composition of a single particle present on the catalyst surface. With reference to SEM micrographs from the surfaces of samples calcined in the range of 450600 C (catalysts AC), it is seen that an increase in calcination temperature up to 500 C caused an increase in particle size from 0.2 to 0.4 m (Fig. 3b and c), after which the particle size decreased to 0.25 m (Fig. 3d). At 500 C, sintering due to Al2 O3 transformation by forming Al2 (MoO4 )3 might play a role in enhancing the particle size. Decrease in particle size at >500 C is probably because of sublimation of MoO3

as reported by Kasztelan et al. [29]. It is seen that at the calcination temperature of 500 C (Fig. 3c), the particle sizes are more uniform, which may lead to efcient reduction of metals during hydrotreating process. This indicates that the optimum calcination temperature may be 500 C. Increase in Ni concentration in NiMo/Al2 O3 catalyst (catalysts B, D and E) did not show any signicant change on the catalyst surface [16]. SEM analysis of NiMoB/Al2 O3 showed that the increase in B concentration in the catalyst (catalysts GI) caused agglomeration of particles (Fig. 4ac). The radial direction analysis (end view) showed that increase in B concentration caused the increase in needle-like crystals [16]. Addition of phosphorus to NiMo/Al2 O3 catalyst (catalyst L) showed irregular particle sizes and agglomeration (Fig. 5b). EDS

Fig. 3. Effects of calcination temperatures on surface morphology of different NiMo/Al2 O3 catalysts: (a) -Al2 O3 , (b) 450 C, (c) 500 C, and (d) 600 C.

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

145

Fig. 4. Effects of B concentration of surface morphology of different NiMo/Al2 O3 catalysts calcined at 500 C for 4 h: (a) 0 wt.% B, (b) 0.5 wt.% B, and (c) 1.1 wt.% B.

analysis indicated the presence of P in these agglomerated particles. The EDS results (Table 3) are based on elemental analysis of selected catalyst particles. It shows that NiMoP/Al2 O3 agrees in concentration values, however, for most of the analysis, the concentrations were completely different from measured values. From this table, 2 wt.% Ni was detected for NiMo/Al2 O3 catalyst calcined at 450 and 500 C, whereas at higher calcination temperature (600 C), Ni concentration was 15 wt.%, probably because of the migration and/or agglomeration of Ni on the surface at 600 C. The Mo concen-

tration obtained from EDS analysis was signicantly higher than that obtained from bulk elemental analysis, indicating that Mo may have migrated as well as agglomerated more on the surface at a given calcination temperature. Boron is a light component and is not detectable from EDS analysis. The concentrations of Ni, Mo, and P for NiMoP/Al2 O3 catalyst from EDS analysis were 3, 14 and 3 wt.%, which are exactly same as the targeted ones. As the EDS analysis is based on a selected particles, it is expected that EDS analysis gives different elemental composition than that in bulk. In summary, the EDS analysis, which is based on elemental

146

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151 Table 3 Summary of EDS analysis of different NiMo/Al2 O3 , NiMoB/Al2 O3 , and NiMoP/Al2 O3 catalysts calcined at 500 C for 4 h Calcination temperature ( C) 450 500 600 500 500 500 500 500 500 500 500 500 500 500
a

Measured by EDS (wt.%) Ni 2.7 2.9 3.0 1.8 2.9 3.1 2.4 2.9 2.6 2.6 2.8 2.5 2.2 3.1 Mo 12.2 13.2 13.2 12.5 13.2 11.1 10.6 13.2 11.7 11.8 9.1 11.8 10.2 12.5 B 0 0 0 0 0 0 0 0 0.5 1.1 1.2 1.3 1.7 P 0 0 0 0 0 0 0 0 2.7

Measured by ICP (wt.%) Ni 2 2 15 4 2 11 7 8 4 3 3 4 2 3 Mo 15 17 25 25 17 27 30 34 17 32 20 24 24 14 B 0 0 0 0 0 0 0 0 n/da n/d n/d n/d n/d 0 P 0 0 0 0 0 0 0 0 0 0 0 0 0 3

Not detectable.

Addition of 0.5 wt.% B to NiMo catalyst caused a decrease in the intensity of the alumina diffraction line, due to the formation of highly dispersed microcrystalline aluminum borate phase on the catalyst surface [30]. With the further increase in boron (1.11.7 wt.%) (catalysts HK), a crystalline borate phase as well as MoO3 phase became more prominent [3133], when the B concentration was increased to 1.7 wt.%. Addition of P to NiMo/Al2 O3 catalyst (catalyst L) did not show any signicant effect on crystallinity of this catalyst, which conrmed the study by Decanio et al. [9]. 3.1.7. Nuclear magnetic resonance Because of the paramagnetic nature of Co and Ni ions, solid state NMR has seldom been used for studying hydrotreating catalyst. To our knowledge, no 1 H NMR analysis for NiMo/Al2 O3 , NiMoB/Al2 O3 and NiMoP/Al2 O3 has been done before. In our case, analysis was performed using dry as well as for air exposed samples. No signicant difference in results was observed. The 1 H NMR spectra of different NiMo/Al2 O3 catalysts containing different Ni, Mo, B and P concentrations calcined at different calcination temperatures (450600 C) are given in Fig. 6. The corresponding NMR peak areas for different catalysts are given in Table 4. Fig. 6 also show the 1 H NMR spectra for support (-Al2 O3 ) for comparison. -Al2 O3 possesses a defective spinal lattice structure, which is terminated by a surface hydroxyl group. During the preparation of catalyst, the metal species interact with the alumina hydroxyl groups to produce dispersed metal oxide phases [34]. Also, new hydroxyl groups can also form on the catalyst surface, which is responsible for the acidity of these catalysts. From NMR analysis, only peak

Fig. 5. Effects of P concentration on surface morphology of different NiMo/Al2 O3 catalysts calcined at 500 C for 4 h: (a) 0 wt.% P and (b) 2.7 wt.% P.

analysis of selected particles on the catalyst surface has limitations in quantifying the catalyst surface composition but gives quantitative data on localized spots on the surface, which may be different from bulk composition. 3.1.6. X-ray diffraction X-ray diffraction (XRD) study was used to detect different crystalline phases present in the catalyst. X-ray diffraction of various calcined NiMo/Al2 O3 catalysts revealed no peaks other than that of alumina (gure not shown), indicating high dispersion of Ni and Mo on the catalyst surface. Increase in calcination temperature from 450 to 600 C (catalysts AC) did not change the crystallinity of the catalyst. These results are in agreement with those reported by Brito and Laine [19].

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

147

Fig. 6. NMR proles of different NiMo/Al2 O3 catalysts. Effects of: (a) calcination temperature, (b) Ni concentration, (c) Mo concentration, (d) B concentration, and (e) P concentration.

at 4.62 ppm was observed for all catalysts. This peak can be attributed to the AlOH group present in alumina [35]. Table 4 shows that there is no signicant change in the NMR peak area with the incorporation of Ni, Mo, B, and P to the support.

3.1.8. Fourier transform infrared spectroscopy Fourier transform infrared (FTIR) spectroscopy in combination with photoacoustic spectroscopy (PAS), is particularly useful to characterize heterogeneous catalysts. Application of this technique to catalysts provides useful

148

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

Table 4 NMR peak area of different NiMo/Al2 O3 , NiMoB/Al2 O3 and NiMoP/ Al2 O3 catalysts calcined for 4 h Ni Support 2.7 2.9 3.0 1.8 2.9 3.1 2.4 2.9 2.6 2.6 2.8 2.5 2.2 3.1 Mo (wt.%) 12.2 13.2 13.2 12.5 13.2 11.1 10.6 13.2 11.7 11.8 9.1 11.8 10.2 12.5 B 0.5 1.1 1.2 1.3 1.7 P 2.7 Calcination temperature ( C) 450 500 600 500 500 500 500 500 500 500 500 500 500 500 NMR peak area (a.u.) 1.9 2.1 1.9 2.0 2.0 1.9 2.1 2.1 1.9 2.1 2.2 2.1 2.2 2.2 2.2

microstructural information that can be correlated with catalytic activity. Each experiment was performed for 23 times. The results were quite reproducible. To study the effects of absorbed water on the catalyst surface properties, FTIR analysis of the calcined (400 C for 3 h) and uncalcined alumina support was performed. Uncalcined sample showed strong band in the range of 30003580 cm1 due to the presence of absorbed water. So, before performing FTIR analysis all catalysts samples were dried in the oven at 400 C for 3 h. FTIR spectra for different NiMo/Al2 O3 catalysts as well as support are given in Figs. 7 and 8. The region 30004000 cm1 in FTIR spectra is termed the hydroxyl stretching region, whereas the region 9001800 cm1 is termed as frequency multiplied range representing the characteristics vibration of AlO and BO stretching. The positions of the hydroxyl bands have been shown to be dependent on the acidity of the hydroxyl group; the basic hydroxyl groups gives rise to the IR bands between 3762 and 3727 cm1 , while the most acidic hydroxyl groups produce bands at 3677 cm1 [9]. FTIR spectra of alumina at 3778

Fig. 7. FTIR spectra of different NiMo/Al2 O3 catalysts. Effects of: (a) calcination temperature, (b) Ni concentration, (c) Mo concentration, and (d) B concentration.

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

149

Fig. 8. Effects of P concentration on FTIR Spectra of NiMO/Al2 O3 catalysts calcined at 500 C for 4 h: (a) 05000 cm1 , (b) 12001500 cm1 , and (c) 28004000 cm1 .

and 3684 cm1 can be attributed to the presence of the most basic hydroxyl group, and the most acidic hydroxyl group, respectively, whereas the band at 3580 and 1670 cm1 can be attributed to the presence of hydrogen-bonded water [6] and the adsorbed water on the catalyst surface [36], respectively. The band at 1100 cm1 , though has not been previously reported in the literature [37,38], represents AlO stretching vibration of alumina [6]. Fig. 8a shows that the incorporation of Ni and Mo on the support caused a somewhat increase in intensity of the bands at 1670 and 1100 cm1 . Fig. 7b shows that the increase in Ni concentration from 1.8 to 3.1 wt.% (catalysts AC) caused a decrease in the intensity of the band at 1670 cm1 and increase in AlO stretching vibration band at 1100 cm1 . However, there was no change in basic and acidic hydroxyl groups with the increase in Ni content in the catalyst. Fig. 7c shows that with the increase in Mo concentration from 10.6 to 13.2 wt.% (catalysts B and F) in NiMo/Al2 O3 , the band intensity at 1670 cm1 , the stretching of AlO vibration (at 1100 cm1 ) and the basic hydroxyl group (band

at 3778 cm1 ) did not change with increase in Mo concentration from 10.6 to 13.2 wt.%. Fig. 7d shows that the addition of B to the NiMo/Al2 O3 increased the intensity of the bands at 1100 and 1408 cm1 . Addition of B resulted in depletion of the IR band at 3778 cm1 , indicating that boric acid reacts with basic alumina [6]. Acid hydroxyl group intensity remained unchanged, whereas intensity of the band at 3580 cm1 increased with the increase in B concentration from 0.5 to 1.7 wt.% (catalysts GK). A new band at 1550 cm1 appeared with the addition of B, due to the formation of Brnsted acid sites, which was conrmed by Decanio and Weissman [6] from FTIR analysis of NiMo/Al2 O3 using pyridine adsorption. This band intensity increased with the increase in B concentration from 0.5 to 1.7 wt.%, which proves that increase in B concentration causes an increase in acidity of the catalyst. The band intensity at 1100 cm1 increased signicantly with the addition of B. A new band at 1480 cm1 assigned to the presence of BO stretching vibration, appeared with the addition of B to NiMo/Al2 O3 , whose intensity increased with the increase

150

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

in B concentration. The band can also be assigned to Lewis acid sites, as indicated by Decanio and Weissman [6]. Fig. 8a shows no signicant effect of P on FTIR spectra. However, when the spectra are enlarged for the range of 12001550 and 28004000 cm1 (Fig. 8b and c), some differences appear. From Fig. 8b, it is seen that the addition of P to NiMo/Al2 O3 catalyst (catalyst L) caused the formation of bands at 1378, 1425, and 1471 cm1 , probably due to the formation of new Lewis acid sites on the catalyst surface. The sharp band at 3666 cm1 (see Fig. 8c) could be due to the OH associated with phosphate [9]. This OH group on the catalyst surface is responsible for the formation of Brnsted acid sites. The bands at 3594 and 3386 cm1 could be due to the formation of new OH groups on the catalyst surface in the presence of phosphorus. 3.2. Implication of the characterization results on HDN activity There was no signicant difference in surface area with the addition of small concentrations of B and P to NiMo/Al2 O3 catalyst. However, increase in B concentration above 1.3 wt.% caused a signicant decrease in surface area. From the literature, it is observed that higher HDN activity is related to decrease in surface area. Lewandowski and Sarbak [7] reported a decrease in surface area and an increase in HDN activity with an increase in B concentration from 2.8 to 6.3 wt.%. Similarly, Jian et al. [15] also reported a decrease in surface area and increase in HDN activity with the addition of 2 wt.% P to NiMo/Al2 O3 . However, it is difcult to correlate the HDN activity with surface area, since HDN activity is dependent not only on the physical surface area but also on the other surface physicochemical properties of the catalyst. Addition of B and P caused a decrease in reducibility of the catalyst. The reducibility of NiMo oxide catalysts favored by their conversions to sulded state is an important factor for the HDN activity. Several attempts have been made to correlate the reducibility of oxidic NiMo catalyst to hydroprocessing activity of their sulded state [25]. It may be noted that in Mo supported catalysts and under normal sulding conditions, OS exchange is a more important reaction than reduction with hydrogen [26]. Thus, it is not generally true that phases more easily reducible are more suldable and/or active after suldation [19]. It is indicated in the literature that high activity for HDN is associated with an increase in the number of acid centers of weak and intermediate strength [8]. From TPD analysis it was observed that addition of B from 0.5 to 1.2 wt.% to NiMo/Al2 O3 catalyst led to the formation of strong acid centers and the further addition of B caused the formation of weak acid centers. So, higher HDN activity can be anticipated from these catalysts. It is known that two types of reactions occur during HDN reaction: (1) hydrogenation and (2) hydrogenolysis. Two catalytic sites have been proposed in the literature to account

for these two types of reaction. These two catalytic sites can be viewed as an equilibrium between Lewis (L) and Brnsted (B) acid sites [39,40]:

Kwart et al. [39] reported that the B-sites are responsible for hydrogenation reactions whereas L-sites for hydrogenolysis. So, B-sites would act as the electron-withdrawing sites for hydrogenation reactions and L-sites would act as the electron-donating sites for hydrogenolysis of Csp2 X bonds [41]. Consequently, high HDN activity of NiMoB/Al2 O3 and NiMoP/Al2 O3 is anticipated because of the formation of new Lewis and Brnsted sites on these catalysts and the acidity of the catalyst would increase with the increase in B concentration from 0.5 to 1.7 wt.%, as is evident from FTIR analysis. It is known that addition of P to NiMo/Al2 O3 has a geometric effect, such as an increase in the number of stacks [42]. When H3 PO4 is used during catalyst preparation, AlPO4 is formed by partial solubilization of Al cations [12], which increases the amount of molybdenum fractions in easily suldable forms, such as multilayered molybdate or MoO3 [10]. Large nitrogen containing compounds, such as heavy gas oil molecules, can better coordinate to the active sites at the top of the MoS2 stacks than to sites close to the Al2 O3 surface [12]. So, it can be anticipated that the HDN activity of B and P containing NiMo/Al2 O3 catalysts will give higher HDN activity of heavy gas oil than those without B and P. The reactivity test of these catalysts will be presented in Part II of this paper.

4. Conclusions A number of NiMo/Al2 O3 catalysts promoted with B and P were prepared and extensively characterized. The maximum BET area of 211 m2 /g was obtained for the catalyst containing 10.6 wt.% Mo and 2.4 wt.% Ni calcined at 500 C for 4 h. In these catalysts, polymolybdenum and tetramolybdenum oxides were predominantly present. Due to the addition of Ni and Mo to support, the acidity on the catalyst surface decreased to some extent. However, the addition of B from 0.5 to 1.2 wt.% to NiMo/Al2 O3 catalyst led to the formation of strong acid centers of intermediate strength and the further addition of B caused the formation of weak acid centers of intermediate strength. SEM-EDS analyses indicated the formation of crystalline B2 O3 and MoO3 due to addition of B, whereas addition of P caused the formation irregular particle size and agglomeration on the catalyst surface. NMR analysis showed the presence of AlOH groups

D. Ferdous et al. / Applied Catalysis A: General 260 (2004) 137151

151

on the catalyst surface. No characteristic peak for BOH was observed for NiMoB/Al2 O3 catalyst. New Lewis and Brnsted acid sites were observed from FTIR analysis of NiMoB/Al2 O3 and NiMoP/Al2 O3 , which complemented the results obtained from TPD analysis.

Acknowledgements The nancial supports to A.K. Dalai from (1) NSERC Collaborative Research and Development Grant, (2) Syncrude Canada Ltd. and NSERC IPS 2 scholarship to D. Ferdous are acknowledged. The authors are grateful to Drs. L.S. Kotlyar and Z. Li at National Research Council, Ottawa, Canada for FTIR and to Mr. P. Abel at Syncrude Research Center, Edmonton, Canada for SEM-EDS analysis.

References
[1] K. Peil, G.L. Galya, G. Marcelin, J. Catal. 115 (1989) 441. [2] J.W. Wang, W.Y. Chen, Catal. Lett. 10 (1991) 297. [3] C. Li, W.Y. Chen, J.S. Yang, C.J. Wu, Ind. Eng. Chem. Res. 32 (1993) 1573. [4] W.Y. Chen, M.C. Tsai, C. Li, Ind. Eng. Chem. Res. 33 (1994) 2040. [5] P. Lulic, Oil Gas Eur. Mag. 26 (2000) 33. [6] E.C. DeCanio, J.G. Weissman, Colloids Surf. A 105 (1995) 123. [7] M. Lewandowski, Z. Sarbak, Appl. Catal. A 156 (1997) 181. [8] M. Lewandowski, Z. Sarbak, Fuel 79 (2000) 487. [9] E.C. DeCanio, J.C. Edwars, T.R. Scalzo, D.A. Storm, J.W. Bruno, J. Catal. 132 (1991) 498. [10] R.C. Lopez, S.G. Lopez, G.L.J. Fierro, A.A. Lopez, J. Catal. 126 (1990) 8. [11] M.J. Lewis, A.R. Kydd, M.P. Boorman, H.P. Van Rhyn, Appl. Catal. A 84 (1992) 103. [12] H. Kraus, R. Prins, J. Catal. 170 (1997) 20. [13] R. Iwamoto, J. Grimblot, Stud. Surf. Sci. Catal. 127 (1999) 169. [14] S. Eijsbouts, M.N.J. van Gestel, R.A.J. van Veen, H.H.V. de Beer, R. Prins, J. Catal. 131 (1991) 412. [15] M. Jian, R. Cerda, R. Prins, Bull. Soc. Chim. Belg. 104 (1995) 225.

[16] D. Ferdous, Ph.D. Thesis, University of Saskatchewan, Saskatoon, SK, 2003. [17] C.Y. Charles, S. Ramanathan, S.T. Oyama, J. Catal. 173 (1998) 1. [18] J. Cruz, M. Avalos-Borja, R.L. Cordero, M.A. Banares, J.L.G. Fierro, J.M. Palacios, A.L. Agudo, Appl. Catal. A 224 (2002) 97. [19] J.L. Brito, J. Laine, J. Catal. 139 (1993) 540. [20] M. Jian, R. Prins, Ind. Eng. Chem. Res. 37 (1998) 834. [21] W.N. Hurst, J.S. Gentry, A. Jones, D.B. McNicol, Catal. Rev. 24 (1982) 233. [22] P. Arnoldy, A.J. Moulijn, J. Catal. 93 (1985) 38. [23] C.Y. Park, S.E. Oh, K.H. Rhee, Ind. Eng. Chem. Res. 36 (1997) 5083. [24] R. Thomas, J.H.V.d. Beer, A.J. Moulijn, Bull. Soc. Chim. Belg. 90 (1982) 1349. [25] R. Burch, A. Collins, Appl. Catal. 18 (1985) 389. [26] P. Arnoldy, M.A.J.v.d. Heijkant, G.D.d. Bok, A.J. Moulijn, J. Catal. 92 (1985) 35. [27] P. Dufresne, E. Payen, J. Grimblot, P.J. Bonnelle, J. Phys. Chem. 85 (1981) 2344. [28] S. Kozai, H. Kabashima, H. Hattori, Fuel 79 (2000) 305. [29] S. Kasztelan, E. Payen, H. Toulhoat, J. Grimblot, P.J. Bonnelle, Polyhedron 5 (1986) 157. [30] T. Curtin, J.B. McMonagle, B.K. Hodnett, Appl. Catal. A 93 (1992) 91. [31] D. Li, T. Sato, M. Imamura, H. Shimada, Appl. Catal. B. 16 (1998) 255. [32] K. Hada, J. Tanabe, S. Omi, M. Nagai, J. Catal. 207 (2002) 10. [33] S.K. Maity, M.S. Rana, S.K. Bej, J. Ancheyta-Juarez, G.M. Dhar, T.S.R.P. Rao, Appl. Catal. 205 (2001) 215. [34] E.C. DeCanio, J.C. Edwards, J.W. Bruno, J. Catal. 148 (1994) 76. [35] L.J. Lakshmi, P.K. Rao, V.M. Mastikhin, A.V. Nosov, J. Phys. Chem. 97 (1993) 11373. [36] L. Pattersson, I. Anderson, L.-O. hman, Inorg. Chem. 25 (1986) 4726. [37] R.A.J. van Veen, M.J.A.P. Hendriks, R.R. Andra, M.G.J.E. Romers, E.A. Wilson, J. Phys. Chem. 94 (1990) 5282. [38] W.-C. Cheng, P.N. Luthra, J. Catal. 109 (1988) 163. [39] H. Kwart, J. Katzer, J. Horgan, J. Phys. Chem. 86 (1982) 2641. [40] S.H. Yang, C.N. Sattereld, J. Catal. 81 (1983) 168. [41] C. Moreau, C. Aubert, R. Durand, N. Zmimita, P. Geneste, Catal. Today 4 (1988) 117. [42] C.R. Ryan, A.R. Kemp, A.J. Smegal, R.D. Denley, E.G. Spinnler, Adv. Hydrol. Catal. 50 (1989) 21.