Fuel Vol 74 No. 8, pp.

1211-1215, 1995
Copyright 0 1995 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0016-2361(94)00042-9 001672361/95/$10.00+0.00

Hydroprocessing of vacuum residues:

relation between catalyst activity,
deactivation and pore size distribution

Mamun Absi-Halabi, Anthony Stanislaus, Tawfic Al-Mughni”,

Shuja Khan* and Arjun Qamra”
Petroleum Technology Department, Petroleum Petrochemicals & Materials Division,
Kuwait Institute for Scientific Research, PO Box 24885, 13109 Safat, Kuwait
“Shuaiba Refinery, Kuwait National Petroleum Co., PO Box 9202, 61003
Ahmadi, Kuwait
(Received 11 July 1994; revised 19 September 1994)

Four catalysts with different unimodal and bimodal pore size distributions having different proportions
of meso- and macropores were studied. The performance of the catalysts in terms of activity and selectivity
as well as deactivation in selected hydrotreating reactions was examined using Kuwait vacuum residue as
feedstock. The effect of catalyst pore size was significantly different for different reactions. For sulfur removal
(HDS), a unimodal pore catalyst with maximum pore volume in the medium mesopore range (10-25 nm
diameter) showed the highest activity. For hydrodemetallation (HDM) and hydrodenitrogenation (HDN)
reactions, large-pore catalysts, having a major proportion of their pore volume in lOt%3OOnmdiameter
pores, were more effective. Bimodal pore catalysts having large amounts of narrow pores showed a higher
rate of deactivation than unimodal pore catalysts with a maximum amount of medium mesopores.

(Keywords: petroleum residues; hydropracessing; catalyst activity)

Catalytic hydroprocessing of residues plays an increasingly
important role in modern petroleum refining1.2. The two
main goals are to increase the distillates output of the
refinery and to improve the quality of the residual fuels.
Both the properties of the feedstock and the catalysts
used in this treatment strongly affect the performance of
the processing units and their economics. Petroleum
residues are complex mixtures of molecular species that
have wide distributions of molecular sizes and high
percentages of heteroatoms, such as sulfur, nitrogen,
vanadium and nicke13.4. The asphaltenic fraction of the
feedstock consists of species having a wide range of
molecular weights5, which varies with the origin of the
crude. Furthermore, the aromatics content of this fraction
also varies between 35 and 50%. Obviously, catalytic
hydroprocessing of such a complex mixture of species
poses a challenging problem to modern petroleum
refining.
The catalysts used in residue hydroprocessing consist
of molybdenum supported on y-alumina and promoted
by cobalt or nickel”. The catalysts have several functions.
They enhance the removal of sulfur, nitrogen and metal
contaminants present in the feed as well as the cracking
of heavier molecules. They also play a major role in
hydrogenating the cracked fragments, leading to an
increase in the hydrogen-to-carbon ratio of the products.
The ability of the feedstock molecules to diffuse
through the catalyst particles to the catalytically active
centres inside the pores is a key factor determining the
effectiveness of the catalyst’. The diffusivity is determined
by the catalyst particle shape and pore structure. The
former property has been thoroughly investigated and
optimum particle shapes and sizes have been determined.
Studies of the effect of pore structure are more limited8-‘2.
Narrow-pore, high-surface-area catalysts usually have
high hydrotreating activity, but lower lifetime owing to
rapid deactivation. The deactivation takes place as a
result of coke and metal (mainly V and Ni) deposition
originating from the heavy feedstockt3-t5. The metal
foulants are usually concentrated near the outer surface
of the pellet, blocking the pore mouths16 and retarding
the access of the reactants to the active sites of the catalyst
within the pores. Hence it has been concluded that it is
important to have wide pores to increase the catalyst’s
stability. However, contradictory results have been re-
ported on the preferred pore structure. The activity and
stability of wide-pore catalysts with either unimodal or
bimodal pore size distribution have been claimed to be
superior by different research groups.
Research aimed at establishing a scientific understand-
ing of the key catalyst properties that influence catalyst
performance in hydroprocessing of Kuwait residues is
underway in the authors’ laboratories. In the present
work, four catalysts with different unimodal and bimodal
pore size distributions having different proportions of
small, medium and large pores were investigated. The

Fuel 1995 Volume 74 Number 8 1211

Hydroprocessing of vacuum residues: M. Absi-Halabi et al.

primary objective was to examine the influence of catalyst temperature was increased to 250°C gradually. Then the
pore size distribution on activity and deactivation in system was purged with hydrogen and pressurized to
HDS, HDN and HDM of Kuwait residual oil. 12MPa. Under these conditions, recycle gas oil was
admitted, for presulfiding using standard procedures”.
When presulfiding was completed, the feed (Table 2)
EXPERIMENTAL was injected at lOOm1h- ’ and the activity test was
Four catalysts in the form of extrudates with different conducted under the following conditions: pressure
pore size distributions were used. The properties of these 12 MPa; LHSV 2 h- ‘; HZ/oil 1000 ml ml- ‘; temperature
catalysts are listed in Table 1. Catalysts PD-Bl, PD-B2 440°C. After 6 h under these conditions, liquid product
and PD-M2 were commercial catalysts from different samples were collected every 48 h for various tests. Feed
manufacturers. Catalyst PD-Ml was prepared in the and product samples were analysed using standard
laboratory from PD-B2 by hydrothermal treatment”. procedures.
The catalysts were characterized according to standard
procedures. Chemical analysis was performed by induc-
tively coupled argon plasma (ICAP) spectroscopy. Pore RESULTS AND DISCUSSION
size distribution was determined by mercury porosimetry. EfSeectof catalyst pore size distribution on activity
A Quantasorb adsorption unit was used for BET surface To assess the effect of catalyst pore size distribution
area measurements. Chemical analysis and physical on activity, two sets of Ni-MO/+)-Al,O, catalysts were
characterization indicated that the chemical composition selected. The first set consisted of PD-Ml and PD-M2
and physical dimensions of the catalysts used were not with unimodal pore distribution. Catalyst PD-Ml is
appreciably different. essentially a macroporous catalyst with 58% of the pore
Activity tests were conducted using Kuwait vacuum volume contained in pores of diameter > 50nm. More
residue as feedstock. A 50ml sample of the catalyst, specifically, -43% of the pore volume is present in the
diluted with an equal amount of silicon carbide, was lOO-300nm diameter pores. Catalyst PD-M2 is a
charged into a tubular reactor. Thermocouples at the mesoporous catalyst with a major portion (-60%) of
centre of the catalyst bed were used to monitor the reactor the pore volume in pores of diameter between 10 and
temperature at various points. After loading of the 25 nm. The second set consisted of PD-Bl and PD-B2
catalyst, the system was purged with nitrogen and the with bimodal pore distribution. Catalyst PD-Bl contains
both meso- and macropores. About 34% of the meso-
Table 1 Properties of the catalysts pores in this catalyst are in the large-diameter (10-25 nm)
range and -20% of the macropores are > 300nm.
PD-Ml PD-M2 PD-Bl PD-B2
Catalyst PD-B2 has a large percentage (55%) of the
Chemical composition (wt%) mesopores in a very narrow range (3-10nm diameter)
MOO, 13.15 11.9 11.6 13.2 and a second set of macropores with a maximum in the
NiO 4.01 2.80 2.52 4.00 range lOO-300nm. TabZe 3 summarizes the meso-
SiO, 0.84 0.02 0.11 0.80 (3-50nm diameter) and macro- (> 50nm) pore size
Physical properties distributions of the catalysts.
Bulk density (g cm- 3, 0.56 0.72 0.55 0.58 The selection of the catalysts represented an initial
Surface area (m’ g- ‘) 85 228 138 312
0.53 0.73 0.76
challenge, owing to the difficulty of securing catalysts
Pore volume (cm” g-r) 0.60
with similar composition. Obviously, the catalyst com-
position has an important effect on reactivity. Hence,
catalysts PD-M2 and PD-Bl were selected with nearly
Table 2 Feed characteristics the same composition, and PD-Ml has identical com-
Test method position to that of PD-B2, since it was prepared from it
by hydrothermal treatment. This choice permits separa-
Density @ 65°C (gcrW3) IP-190 0.9827 tion of the effect of composition from that of pore
API gravity (API) D-1250 7.8 structure.
Sulfur (wt %) XRF 5.2
Nitrogen (wt%) Kjeldahl 0.44
The hydrodesulfurization activities of the four catalysts
CCR (wt%) IP-13 19.2 with different pore size distributions are compared in
Asphaltenes (wt%) IP-143 9.21 Figure 1. These data show that catalyst PD-M2, which
Viscosity @ 100°C (mm s- ‘) IP-71 701.2 has a unimodal pore size distribution with a large
Nickel (ppm) ICAP 26.3 percentage of medium-size mesopores (l&25 nm) is more
Vanadium (ppm) ICAP 93.8
effective than the others for promoting the HDS reaction.

Table 3 Meso- and macropore distributions in catalysts

Pore Mesopore distribution (%) Macropore distribution (%)

volume
Catalvst (cm3a-‘1 3-10nm 10-25 nm 25-50 nm 5GlOOnm lOO-300nm >3OOnm

PD-M 1 0.60 4 11 27 15 43 0
PD-M’ 0.53 38 60.5 1.5 0 0 0
PD-BI 0.73 7 34 19 6 16 18
PD-B2 0.75 55 8 8 6 21 2

1212 Fuel 1995 Volume 74 Number 8


The activity for HDS decreases with increasing pore size.
Thus the macroporous unimodal catalyst PD-Ml with
58% pore volume in pores > 50 nm diameter shows the
lowest HDS activity. Of the two bimodal pore catalysts
(PD-Bl and PD-B2), PD-B2 with a larger percentage
(55%) of narrow mesopores (3-10nm) than PD-Bl
exhibits a higher activity and ranks second in the series.
The ranking of the four catalysts for HDS is
PD-M2 > PD-B2 > PD-Bl > PD-M 1
The activity of hydroprocessing catalysts is known to
be affected by both surface area and composition.
However, no correlation can be observed between the
HDS activity trend and either of these properties. For
example, PD-M2 has lower MO and Ni contents and a
lower surface area than PD-B2, yet it is the most active
catalyst, Hence the differences in activity can mainly be
attributed to the pore structure. To account for this
observation it should be noted that reactions occurring
during the hydroprocessing of heavy oils are strongly
influenced by diffusional effects. Two factors control these
effects: the pore size of the catalyst and the molecular
size distribution of the feedstock.
Increasing the pore size of the catalyst, which is
normally accompanied by a decrease in surface area,
improves diffusion. For maximum activity, it is desirable
to have maximum possible surface area compatible with
the absence of diffusional limitations. A compromise
30 I
0 40 -&e or%rea’:
Figure 1 Hydrodesulfurization activities
catalysts
PD-Ml PD-MS PD-81
Figure 2 Catalyst activities in vanadium and nitrogen removal
Hydroprocessing of vacuum residues: M. Absi-Halabi et al.
between surface area and pore diameter is essential in
selecting catalysts for residue hydroprocessing. The
requirements may however be different for different
reactions and different feedstocks. For hydrodesulfur-
ization of Kuwait vacuum residue, a catalyst (PD-M2)
with a pore maximum in the 10-25nm diameter range
and a surface area of 228 m2 g- ’ is very effective. This
indicates that in this pore diameter range, diffusion
restrictions are absent and the catalyst surface area is
utilized maximally in promoting the HDS reaction. In
contrast, catalyst PD-B2 has a significantly higher surface
area (312 m2 g- ‘), but most of its pores have diameters
< lOnm, which indicates that diffusion effects are pre-
dominant, restricting the access of larger feedstock
molecules, as reflected by the low HDS activity. An
increase in pore size would improve diffusion but might
decrease the surface area significantly. This would lead to
a decrease in HDS activity, as noted for the wide-pore
catalyst PD-M 1.
Figure 2 shows the results for vanadium removal at
mid-run. The observed order of activity is
PD-M 1 > PD-M2 > PD-B2 > PD-Bl
It is seen that the large-unimodal-pore catalyst (PD-Ml),
which contains a major proportion of its pores in the range
10&300 nm diameter, has the highest activity for vanadium
removal. The next highest activity is shown by the
unimodal mesopore catalyst (PD-M2). The activity of the
bimodal catalyst PD-B2, which contains a large propor-
tion (- 55%) of narrow pores (3-10 nm) and N 20% pores
with diameter 100_300nm, is higher than that of the
+ Catalyst PD-MI
large-pore bimodal catalysts PD-Bl, but lower than that
. Catalyst PD-BI
of the unimodal mesopore catalyst PD-M2. It appears
that very large pores (e.g. > 300nm) are of little value
for various hydrotreating reactions, including HDM.
It is generally known that the metals in petroleum
residues are present in large porphyrinic structures.
Diffusion of such large metal-bearing molecules is
relatively low if the pores are narrow. Hence for HDM
reactions the catalyst activity is relatively independent of
the surface area if the pores are relatively narrow.
Wide-pore catalysts with adequate surface area would
be expected to be more reactive. The results obtained in
this study confirm this conclusion.
I
The activities of various catalysts for nitrogen removal
200 240
from the residual feedstock (HDN reaction) are also
(h) compared in Figure 2. The HDN activities of the catalysts
differ considerably and are in the order
and deactivation of the
PD-B 1 > PD-M 1 > PD-M2 > PD-B2
This trend is parallel to the percentage of pores with
diameters > 1Onm. From T~h/e 3 it can be seen that the
avanadium
total percentage of pores > 1Onm is 93, 96, 62 and 45%
0 Nitrogen
for PD-Bl, PD-Ml, PD-M2 and PD-B2 respectively.
Hence, it appears that HDN takes place mainly in the
meso- and macropores. Since nitrogen in residual oils is
present predominantly in large porphyrinic structures,
large-pore catalysts would be expected to be more
effective in its removal.
_E@ct Qfccitcilj~stpore size on decictiurtion
In an attempt to correlate the deactivation tendency
:c of catalysts with pore size distribution, the used catalysts
PD-B2 at the end of various runs were characterized. Tub/e 4
summarizes the results for carbon and vanadium deposits
Fuel 1995 Volume 74 Number 8 1213
Hydroprocessing of vacuum residues: M. Absi-Halabi
Table 4 Concentrations of carbon and vanadium deposited on
catalysts
Loss of
Carbon Vanadium surfdce Loss of pore
Catalyst (wt%) (wt%) area (%) volume (%)
PD-M 1 15.5 11.0 20.5 36.5
6.8 39.1 55.0
PD-M2 15.8
PD-Bl 19.7 9.6 44.5 67.0
PD-B2 21.2 8.7 50.0 80.0
formed on the catalysts and the loss of surface area and
pore volume. The percentage of carbon deposited was
found to correlate well with the total pore volume of the
fresh catalysts. As the total pore volume increased, less
carbon was deposited. Furthermore, the percentage of
carbon was observed to increase as the percentage of
pores > 25 nm decreased.
These data suggest that large molecules that have high
coke-forming tendencies, such as asphaltenes, spend more
time within the narrower pores of the catalysts, owing
to slow diffusion of reactants and products. This leads
to further cracking and the formation of coke. Hence,
catalysts with a high percentage of macropores facilitate
diffusion and have less tendency to form coke.
Another interesting point is that catalyst PD-M2,
which has a monomodal pore size distribution with
maximum in the lo-25nm diameter range, also shows
low coke formation similar to the large-pore catalyst
PD-Ml. As discussed earlier, this range of pore size is
large enough for the free diffusion of a large proportion
of low-molecular-size asphaltenes and other heteroatom-
containing species that can undergo various reactions on
the catalyst surface within the pores. The products formed
in the reaction can also desorb and diffuse out of the
pores easily.
The high hydrogenation activity of the catalyst may
also be partly responsible for the low coke deposition.
Coke precursors such as olefins, carbonium ions and
resin-type polycyclic aromatics may be hydrogenated to
saturates by the strong hydrogenation function of the
catalyst and consequently may reduce coke formation.
A large amount of saturated hydrocarbons was noticed
in the products with this catalyst, confirming its high
hydrogenation activity.
The vanadium concentrations on the spent catalysts,
presented in Tuble 4, show that catalyst PD-Ml,
which has the highest HDV activity, accumulated more
vanadium than the others. Furthermore, this catalyst
showed the most uniform vanadium concentration
distribution throughout the pellet cross-section. On the
other hand, catalyst PD-M2 showed lower vanadium
deposits, and vanadium was mostly located on the outer
edges of the catalyst. For the bimodal catalysts, catalyst
PD-Bl, which has a higher percentage of macropores,
had a more uniform vanadium distribution across the
pellet than catalyst PD-B2.
Vanadium distribution within the pellet is an indicator
of the extent of the diffusion efficiency of vanadium-
containing species into the catalyst. For PD-Ml, which
has > 60% of its pore volume in pores of large diameter,
diffusion of large vanadium-containing species is almost
unrestricted”. As a result, hydrodevanadation occurs
throughout the pellet. In the catalysts with narrower
1214 Fuel 1995 Volume 74 Number 8
et al.
pores, such as PD-M2 and PD-B2, the large molecules
have limited access to the internal pores of the catalyst
pellets; hence the demetallation reaction occurs at the
pore entrance. This results in vanadium deposition at the
pore entrance, restricting further diffusion.
The percentage reductions in pore volumes and surface
areas for the four catalysts (Tub/e 4) are in the order
PD-B2 > PD-Bl > PD-M2 > PD-M 1
This trend is evidently due to the fact that pore volume
and surface area losses are caused by deposition of coke
and foulant metals. In catalysts with large amounts of
small pores, the deposited metals can cause plugging of
pore mouths, leading to large losses of both surface area
and pore volume. In larger-pore catalysts, on the other
hand, the foulant metals and coke are deposited more
evenly throughout the catalyst pellet; hence the reduction
in pore volume and surface area is expected to be low.
The pore size distributions of the four catalysts and the
above trend conform with the above argument.
CONCLUSIONS
The results revealed that the effect of catalyst pore size
was significantly different for different reactions. For sulfur
removal, a unimodal-pore catalyst with maximum pore
volume in the medium-size mesopore range (1625 nm
diameter) showed the highest activity. For HDM and
HDN reactions, large-pore catalysts having a major
proportion of the pore volume in lOO-300nm diameter
pores were more effective. An increase in the proportion
of large macropores (> 300nm) did not confer any
advantage. Bimodal pore catalysts having a large amount
of narrow pores showed a higher rate of deactivation
than unimodal-pore catalysts with a maximum amount
of medium-size mesopores.
ACKNOWLEDGEMENTS
The authors thank the KNPC and KISR managements
for their encouragement and financial support. They also
thank the staff at the Petroleum Evaluation Facility
(PEF), the Central Analytical Laboratory (CAL) and the
Catalyst Characterization Facility (CCF) at KISR for the
analyses of feed, products and catalysts.
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Fuel 1995 Volume 74 Number 8 1215