PII: SOO16-2361(98)00015-5

Fuel Vol. 77, No. 11, pp. 1221.1227, 1998

0 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0016.2361/98 $19.00+0.00

Catalytic upgrading of petroleum

residual oil by hydrotreating
catalysts: a comparison between
dispersed and supported catalysts
Koh Peck Tian, Abdul Rahman Mohamed

and Subhash Bhatia*

School of Chemical Engineering,

Universiti sains Malaysia,
31750, Tronoh, Perak Darul Ridzuan, Malaysia
(Received 28 April 1997; revised 19 September
1997)

Perak Branch Campus,

Seri Iskandar,

Hydrogenation of residual oil with a viscosity of 225 centipoise at 45.4C was carried out in the presence of
dispersed water soluble Ni-Mo catalyst and alumina supported CO-MO catalyst in order to compare their
hydrotreating activities. The experiments were conducted in batch mode under a pressure of 7 MPa of H2 and
340C using a 300 ml high pressure stirred reactor. The results revealed that presulfidation treatment of the
supported CO-MO catalyst was important. Hydrodenitrogenation (HDN) of residue over dispersed water soluble
Ni-Mo was compatible with that of a commercial presulfided Co-Mo/AlzOj catalyst. A longer reduction time
was effective for reduced Co-Mo/AlzOj catalyst in hydrodesulfurization (HDS) and HDN activities. Longer
reaction time also increased the dispersed catalyst performance. 0 1998 Elsevier Science Ltd. All rights reserved
(Keywords: residual oil; hydratreating;

dispersed catalyst)

INTRODUCTION

As the worlds supply of light sweet crude oil is depleted

and there is an increasing demand for transportation fuels
such as gasoline, the stock of heavy oil and residue from
petroleum fractions has become more important as a
component in supplying demands for fuel and petrochemical feeds. Therefore, the combination of higher fuel prices
and environmental constraints has focused attention on the
upgrading of residue.
The general chemical objectives of upgrading processes
are.

(1) Convert high molecular weight residue components to

distillates with a boiling range below 300C. This conversion requires breakage of the C-C and C-S bonds in
the residue fraction with mild hydrocracking in the
presence of acid catalyst.
(2) Increase the H/C ratio of the distillate products from 1.5
in the feed toward 1.8 mol mol- as required for transportation fuels. This is essentially done by adding
hydrogen (hydrogenation) and breaking the molecular
bonds (cracking).
(3) Remove the heteroatoms such as sulfur and nitrogen
down to acceptable levels to comply with environmental limits.Catalysts that have been developed for
hydrotreating processes include MO, W, Co, Ni, V and
Fe. The degree of dispersion and size of catalyst
*Author to whom correspondence
Fax: 605-3677055;

should be addressed. Tel: 605-3677572;

Email: kkbhatia@kimia.eng.usm.my

particles strongly affect its activity. A well-dispersed

catalyst should favour rapid uptake of hydrogen to
prevent free radical condensation leading to coke
formation. High levels of catalyst dispersion can be
achieved by introducing either finely divided powder
or water-oil soluble catalyst precursors in the feed2.
Commercial hydrogenation catalysts for residue upgrading are mixtures of CO-MO or Ni-Mo, supported on
alumina and formed into pellets or beads. The active metals
are mostly in the sulfide form, with Co or Ni acting as a
promoter on crystallites of MO& to improve hydrogen
adsorption3. Sulfided MO, CO-MO and Ni-Mo catalysts
used in hydrodesulfurization @IDS), hydrodenitrogenation
(HDN), and hydrodemetallization (HDM), are prepared by
impregnating catalyst extrudates with a solution of Co, Ni
and MO followed by drying, calcination at 400-5OOC, and
sulfiding with H2S/H2 at 3.50-400C.
Mohamed4 observed that water dispersed NHz2-MO
catalyst is effective compared to supported catalysts in
hydrocracking of residual oil. Chen and Tsa? used the TPR
(temperature programmed reduction) method to monitor the
molybdenum oxide support interaction. They found that at
moderate temperatures the reduction peak is the octahedrally Mo6 multi-layer which is responsible for HDS
activity. The relatively high temperature reduction peak
indicates strong interaction between the carrier and the MO
species which implies higher hydrogenation ability. This is
the octahedrally and tetrahedrally Mo6+ mono-layer
species. Besides that, Ranke16 claimed that sulfided NiW/alumina produced
> 60% conversion, 1% coke

Fuel 1998 Volume

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11

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Catalytic upgrading of petroleum residual oil: K. P. Tian et al.

formation and good demetallation and desulfurization for

slurry hydrocracking at 538C. Landau er al7 found that
Ni-MO-Al has higher hydrogenation activity for aromatics
than Co-MO-Al and bulked Ni-Mo displays better
activity than alumina supported catalysts in hydrogenation
routes.
Lee and Yoon* investigated the optimum metal composition of CO-MO dispersed catalyst in HDS activity.
Dispersed catalyst shows higher conversions and selectively
promoted activities towards hydrotreatment compared to
supported catalyst. The maximum promotion appeared at a
catalyst composition correspondin to a Co/(Co + MO)
atomic ratio of 0.3. Sanford and Xu studied the relationship
between solid formation, residue conversion, liquid yield
and losses in the presence of a variety of chemicals in
hydrotreating Athabasca Bitumen with commercial Ni-Mo/
y-alumina. They found that generally there was no
difference between sulfided and presulfided catalyst.
Moreau and Benyamna found that temperature is the
most important factor even at low pressure and shorter time
in the HDS process. H2 pressure is more significant in HDN
processes while CO-MO rich mixtures are more efficient for
HDS and HDN activities.
It is difficult to generalize the results reported in the
literature to other systems. The objective of the present work
is to study the hydrogenation of residual oil using a water
soluble dispersed Ni-Mo catalyst as an alternative to a
commercial supported CO-MO catalyst, which is in powder
form. The effects of pretreatment methods such as reduction
and sulfidation of CO-MO catalyst were studied for
hydrotreatment activity. A study of the effect of reaction
time and pretreatment time on the hydrogenation reaction
was also undertaken. A comparison between the performance of dispersed catalyst over supported catalyst for
hydrotreating was made.
EXPERIMENTAL
The residual oil used in this study is low sulfur waxy
residue refined by Petronas Petroleum Refinery, Melaka,
Malaysia. The properties of the residue are presented in
Table 1.

Table 1

Analysis of residual oil

Viscosity at 45.4C
Speed (rpm)
Viscosity (cp)

50
112

Element composition
Carbon
Hydrogen
Nitrogen
Sulfur
H/C atomic ratio
Distillation
Vol%
5
10
20
30
40
50

30
131

20
156

10
225

2
653

5
338

analysis (wt%)

87.43%
10.61%
1.25%
2.32%
1.46

analysis
Temperature
API
density
42.0
37.2
29.0
23.0
17.8

205
215
220
240
280
370

Fuel 1998 Volume

77 Number

The catalysts used were alumina supported CO-MO and

dispersed Ni-Mo based catalyst. Co-Mo/AlzO3 (0402T) is
a commercial catalyst from Harshaw Chemical Company,
USA. The composition of Co-Mo/Alz03 is Si 2.1%, Co
1.9%, MO 8.6% and Al 37.4%. Ni-Mo dispersed catalyst
was prepared from a solution of nickel chloride and
ammonium molybdate in 0.5 molar ratio according to the
optimum finding by Anderson and Yuen. This ratio is
similar to that found for the commercial Ni-Mo Shell 424
catalyst. Both chemicals were of analytical grade and
supplied by BDH, UK.
The supported Co-Mo/Alz03 has to be pretreated to
increase its performance. These comparative pretreatment
methods are: (1) calcination, where the catalyst was heated
at 400C under air flow for 4 h in a furnace; (2) reduction,
where the catalyst was held at 400C under hydrogen flow at
30 psig and 100 ml min- for 4 h, and (3) presulfidation, the
catalyst was treated with excess powdered elemental sulfur
where the mixture was loaded in a quartz tube reactor,
heated from room temperature to 360C with temperature
programmed steps under hydrogen flow7.
Experimental apparatus and set-up

Experiments on residual oil were conducted in a batch

mode with the assembly set-up shown in Figure 2. The high
pressure 300 ml reactor was supplied by M/S Parr
Instrument Company, USA, and is capable of handling
pressure up to 14 000 kPa and a temperature of 350C. It is
equipped with a temperature controller and a stirrer with
speed controller.
A one-way check valve is fitted in the gas line to prevent
any reverse flow, while a three-way valve is fitted between
two gas cylinders of Hz and N2. A pressure gauge is
mounted with a gas release valve to check any leak in the
system as a safety measure. An internal cooling coil is
installed to provide an effective means for controlling
temperature overshoot in the reactor.
Experimental procedure

A residue sample was mixed with catalyst and poured

into the reactor. After purging with nitrogen, the valve
connected to hydrogen gas was opened to develop a total
hydrogen atmosphere. The reactor was heated to 340C at
the rate of 350C h-l. The zero reaction time was defined
when the reactor working temperature (340C) and pressure
(7 MPa) were attained. The stirrer speed was maintained at
1000 rpm for reaction. The reaction was carried out for a
fixed period of time. The reactor was cooled down to room
temperature and purged with nitrogen at the end of the run.
The liquid product oil was collected for analysis. The bomb
and stirrer assembly were washed with dichloromethane.
The oil-dichloromethane washings were recovered by
using a rotary evaporator.
Analysis of product

range (C)

Source: Petronas Petroleum Refinery, Melaka, Malaysia

Name: Low Sulfur Waxy Residue
API density: 18.4API

1222

1
1210

Catalysts preparation and pretreatment

11

Different analytical procedures were carried out to

determine the composition of the feed and products of the
hydroprocessing reaction.
Viscosity was obtained by testing with a spindle type
viscometer model DV-111 Rheometer that was supplied by
M/S Brookfield Engineering Laboratories, USA. The testing
was carried out at 4SC, the minimum temperature at which
the residue exists in liquid phase. The viscometer was fitted
with a provision for operating at different controlled

Catalytic upgrading

chedcvalve

of petroleum

gasproduct
exhaust

Needle valve

residual oil: K. P, Tian et al.

needle valve
Cooling

gas inlet

-..&Lii&_

Cooling

3-way valve PI
0-l

regulator

PI
0

Temperature
controller

N2

i
-..Nitrogen
Cylinder

Hydrogen
Cylinder

Figure 1

Table 2

Schematic

Effect

diagram

of catalyst

of experimental

pretreatment

set-up

on product

catalyst

distribution

Reduced catalyst

Calcinated

[31

[41

catalyst

Without
catalyst
Ul

Presulfided

Run No.
Catalyst

1
-

13
12
Co-MO/alumina

11

15
14
Co-MO/alumina

4
2
Co-MO/alumina

Run time
(min)

30

30

240

30

240

30

PI

120

Product distribution
1st drop (C)

(~01%)
170

< 170C (naphtha)

< 190C (kerosene)

160

155

120

170

4.9

10.8

15.1

16.7

14.2

< 220C (jet fuel)

32.5

31.6

< 250C (diesel)

20

17

32.4

29.9

> 250C (gas oil)

Elemental composition

(wt%)

157

140

Dispersed catalyst
PI

120

185

170

4.6

10.9

15

13.2

8.8

10.8

20.7

21.1

21.5

11

38

33.9

31.6

36.7

30.4

26.3

30.4

29.6

22.1

57.8

3
Ni-Mo

240

30

120

240

165

166

2.7

3.5

16.5

5.2

8.2

23.6

10

19.3

21.5

20.2

23.3

49.4

21.7

32.2

40.7

32.7

36.1

37.6

40.1

28.7

17

4.4

149

144

C%

85.0

84.74

84.09

83.2

83.56

82.2

85.6

83.8

84.8

84.9

84.78

84.7

86.17

H%

12.39

12.79

13.01

13.2

12.76

12.65

13.25

12.1

12.8

12.9

12.52

13

13.37

N%

1.14

1.13

0.92

0.35

1.13

0.89

0.55

1.03

0.68

0.65

1.03

0.65

S%

2.06

1.43

1.43

1.34

1.49

1.46

1.43

1.93

1.92

1.82

1.95

1.92

1.34

WC ratio

1.749

1.811

1.854

1.91

1.832

1.847

1.857

1.76

1.82

1.83

1.772

1.84

1.862

Viscosity

0.49

(cp) (45.4C)

lrpm

666

435

315

230

333

320

255

499

448

435

678

327

10 rpm

210

108

98

82

124

104

92

140

126

124

168

108

85

50 rpm

110

72

55

49

73

70

66

92

87

79

106

57

47

290

T = 34OC, P = 7 MPa, residue = 45 g, catalyst loading = 0.3 wt%

Fuel 1998 Volume

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11

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Catalytic upgrading of petroleum residual oil: K. P. Tian et al.

temperatures. The PE2400 Series II CHNS Element

Analyzer supplied by M/S Perkin Elmer Co., USA was
used to determine the weight percentage of C, H, N and S in
organic samples. The analysis technique was based on the
combustion in a pure oxygen environment. ASTM distillation was done to determine the product boiling range
distribution after hydrocracking in the experiment.

1.95

1.85

Experimental design

Experiments were carried out in the 300 ml high pressure

batch reactor operating at 340C and 7 MPa of hydrogen
pressure. For comparative purposes, the selected operating
conditions corresponded to industrial process conditions.
The reaction conditions were held constant throughout the
study.
Prelimin~ test runs were conducted to ensure that the
equipment was functioning properly. A test run without
adding any catalyst was performed to investigate the effect
of thermal cracking. A number of runs were carried out for
different types of catalyst pretreatments and reaction times
in a randomized sequence. The results obtained with
different catalyst pretreatments are presented in Table 2.
The experimental responses were the percentage of
heteroatom content reduction which indicates the hydrodesulfurization and hydrodenitrogenation. The atomic ratio
H/C was indicative of the hydrodearomatization step or
hydrocracking reaction. The liquid product viscosity
reduction was indicative of the visbreaking steps and the
ASTM distillations were carried out to interpret the
selectivity of the conversion.
The percentage of sulfur removal in hydrodesulfurization
is given by
%HDS = ([S,,] - [S,])/[S,,]

X 100%

(1)

where [S,] is the sulfur content of the residue and [S,] the
product.
RESULTS AND DISCUSSION
Effect of catalyst pretreatment
The effect of catalyst pretreatments were studied based on
the Co-MO/alumina catalyst by comparing the presulfided
with the reduced catalyst. The effect of thermal cracking
without catalyst was 11.2% of HDS, which reduced sulfur
from 2.32 to 2.06 wt%. Untreated catalyst without pretreatment removed 21.6% of sulfur while the reduced catalyst
resulted in 38.4% removal. The presulfided catalyst gave
better effect on the heteroatom removal compared to
reduced catalyst at the same operating conditions. It gave
42.4% of the overall HDS as shown in Figure 2. High
asphalt content or aromatics in the waxy residue hinders
catalyst activity. HDS activity can be increased by
increasing the temperature.
If sulfur is in the form of lateral chains or monocyclic
structure, it will be readily accessible to hydrotreating12.
Presulfided Co catalyst has higher surface area in sulfide
sites and is finely dispersed in the MO phase to increase the
activity of heteroatom. The effect of thermal cracking
without catalyst activity is 9% HDN. Reduced catalyst
removed 56% of nitrogen. Presulfided catalyst reduced the
nitrogen content down to 0.35 wt% which is 72% of the total
nitrogen atoms.
The sulfided catalyst was more effective than reduced
catalyst in HDN. Pretreatment with hydroce? and H%!
caused partial reduction and replacement of 0 - ions by S

1224

Fuel 1998 Volume

77 Number

11

ii

2
3

3
m

1.65

1.55

1.25I_,,__,
0

Reactiontime (hr)

Figure 2 Sulfur
supported catalyst

removal

over dispersed

and presulfided

ions (Moo3 - MO&). If Moo3 is first reduced to MoOz, it

is difficult to sulfide, and considerable oxygen may remain
in the catalyst. Such a catalyst may be considerably less
active than a proper sulfided catalyst and may show
different reaction selectivity. Mo$ has a layer structure
with weak interactions between the sulfur atoms in adjacent
layers. Most of the cobalt is adsorbed onto the edges of the
MO& crystallites or is present as Co& crystallites on the
support. Some cobalt can also occupy tetrahedral sites in the
y-Al203 lattice which is inactive. A high CO-MO ratio and
high sulfidation temperature favours formation of CogSs3.
The sites for HDN are assumed to be associated with anion
vacancies on the crystal edge13. HDN reaction takes place at
the oxidic and sulfidic form of the catalyst. Thus, the
percentage of nitrogen removal was higher than sulfur
removal.
Hydrodearomatization is hydrogenation of aromatics
followed by cracking and ring-opening reactions. The
degree of activity is indicated by the H/C atomic ratio.
The high viscosity of residue is thought to be due to
entanglement between the high molecular weight components of the oil and also the formation of ordered structures
in the liquid phase14. Visbreaking is a mild thermal cracking
activity which is believed to remove side chains of the
asphaltenes and break the bridgin aliphatic linkages, thus
reducing the viscosity of the feed I%.
Noncatalytic thermal reaction caused a 20.1% increment
of the H/C ratio from 1.46 to 1.75, while viscosity reduced
from 225 to 210 cp (6.7% decrease). Untreated catalyst
increased the H/C! ratio to 1.83 (25.4% of increment) and
with 45% viscosity reduction (124 cp). With sulfidation
treatment, the H/C ratio was increased drastically to 1.9
(30.9%) with the viscosity reduction 64%. As compared to
the reduction treatment, the H/C ratio was only increased up

Catalytic

tNi-Mo@ispersed)

+Co-Mo(sulfidcd)

0.4 I

upgrading

of petroleum

residual

oil: K. P. Tian

et al.

to 1.86 with the reduction of viscosity about 59%. Breaking

of C-C bonds depended on carbenium ion intermediates,
which were promoted by the acid site on the catalyst.
Hydrogenation of aromatics on sulfide catalyst takes
place by a similar mechanism as hydrodesulfurization, first
involving electron donation by Mo3+ then proton donation
from SH- groups associated with Co3. The anion vacancy
necessary to allow formation of such a species might be too
small to accommodate larger aromatic molecules. These
would then be adsorbed on the edge, perpendicular to the
surface or flat in positions; where enough room could be
made by removal of more contiguous sulfur atoms, would
result from application of higher hydrogen partial pressures.
Selectivity was varied at different reaction times under
different types of catalyst activities. For sulfided catalyst
(4 h reaction), 10.8 ~01% of lighter product with boiling
point < 170C was produced. The total middle distillate
(b.p. < 220C) yield (35.8 ~01%) was lower than with 2 h
reaction time (53.2%). Reduced catalyst gave higher middle
distillate selectivity (41.2%) in 4 h reaction time. Therefore,
sulfiding of the surface structure on the catalytic site is not
required for hydrocracking of highly condensed saturated
hydrocarbons. The effect of catalyst pretreatment on
product selectivity was not significant compared to reaction
temperature and pressure. The variation of results depended
on the phases generated in the system and the relative
importance of hydrogenation activity involved.
Effect of catalyst combination and its support

Reactiontime (hr).

Nitrogen removal over dispersed and presulfided

supported catalyst

Figure 3

Ni-Mo (Dispersed)

+-Co-MO

(slllfidcd)

Reaction time (hr)

4 Hydrocracking over dispersed and presulfided

supported catalyst

Figure

Hydrogenation of residual oil was carried out with two

types of catalyst combinations for activity comparison, i.e.
CO-MO supported by alumina and water soluble dispersed
Ni-Mo catalyst.
At 4 h reaction time, the sulfur content of residue was
reduced to 1.3 wt% from 2.32 wt% (42.4% removal) by
water dispersed Ni-Mo catalyst. Simultaneously, the
nitrogen content was reduced from 1.25 to 0.49 wt% as
shown in Figure 3. The present study is compatible with that
of Moreau and Benyamna, who found that Ni-Mo rich
mixture catalyst exhibits better activity for HDS and HDN
than CO-MO rich mixture catalyst.
In Figure 4, water dispersed Ni-Mo increased the H/C
ratio from 1.56 to 1.86 (27.9% increment) with 62.2% of
viscosity reduction. This number is low as compared to
sulfided CO-MO alumina support catalyst (H/C ratio of
1.90). The presence of water increased the hydrogen partial
pressure which accelerated the I-IDN activity instead of
hydrocracking reactions. Thus, the long chain molecule was
not completely cracked into lighter compounds.
The sulfided Co-MO/alumina
catalyst produced
10.8 ~01% of naphtha range material and this fraction
decreased to 3.5 ~01% when dispersed Ni-Mo is used.
Comparison of these product distributions are shown in
Figure 5. It is probable that the complex component was not
completely cracked as reported by Ranke16. The initial step
in the conversion of residue to lighter products involves free
radical cracking. The free radicals and olefins resulting from
this cracking are very reactive and can recombine to form
coke15. Stable oil and gas products resulting from primary
cracking of residue can also undergo free radical cracking
and thus generate additional free radicals and olefins. These
can further react to form gas and coke unless a source of
reactive hydrogen is available.
The dispersed catalyst system has been developed mainly
for the hydroconversion of heavier to lighter oils. There
is a need to improve the activity and selectivity for a

Fuel 1998 Volume

77 Number

11

1225

Catalytic upgrading of petroleum residual oil: K. P. Tian et al.

W% Naphtha

0% let Fuel
??
% Diesel

W%Gasoil

CO-MO
(sulfided)

Ni-Mo
(Dispersed)
Catalyst type

Product distribution over dispersed and presulfided

supportedcatalyst

Figure 5

Table 3

Effect of reduction period on product distribution

Reduced Co-MO/alumina

Run No.
Reaction time (h)
Reduction time (h)

5
6
4
4
no treatment2

Product distribution
1st drop (C)
< 170C

(~01%)
165
5.0
< 190C
16.5
< 220C
19.3
< 250C
21.7
> 250C
37.6
Elemental composition (wt%)
C%
84.91
H%
12.93
N%
0.65
S%
1.82
H/C ratio
1.827
Viscosity (cp)
lrpm
435
10 rpm
124
50 rpm
79

catalyst
7
4
4

158
5.0
5.6
24.4
33.9
31.1
84.98
13.09
0.61
1.56
1.848
390
100
68

10
4
6

140
10.9
8.8
21.5
36.7
22.1
85.6
13.25
0.55
1.43
1.857
255
92
66

149
8.9
22.6
21.8
27.5
19.2
84.1
13.1
0.44
1.42
1.869
237
90
61

T = 340C. P = 7000 kFa, residue = 45 g, catalyst loading = 0.3 wt%

hydrotreatment reaction such as HDS. A dispersed catalyst

system has a number of characteristic advantages over
supported catalysts26; i.e. little deactivation, high
inhibition of coke formation, resulfiding from maximum
interaction of oil and hydrogen with the catalyst, and a high
degree of catalytic metal utilization due to the absence of
diffusional limitation. The dispersed catalyst is highly
active due to large specific area and it is sufficiently small

1226

Fuel 1998 Volume

77 Number 11

to be readily dispersed in the residual oil. Moderate amounts

of Ni and V can be deposited on the catalyst surface without
deactivating the catalyst. However, there are few disadvantages. First, a well dispersed catalyst should favour rapid
uptake of hydrogen, to prevent the free radical condensation
that would lead to coke formation17. Second, dispersed
catalysts generated in situ from the precursors in the reactant
mixture are difficult to recover and are therefore only used
once.
Selection of catalyst combination

Nickel displays a high activity in aromatic ring and

cyclohexane hydrogenation7. In residue oil the fraction of
aromatic carbon content ranges from 0.3 to 0.44. Nickel is
effective for complete hydrogenation and increasing WC
ratio. It might not be economical for commercial
processes because of higher hydrogen consumption for
hydrogenation. This problem can be overcome by small
atomic ratio of Ni/Mo content in the catalyst ( < 0.5)*.
The Ni2+ ion diffuses more rapidly than the Co2+ ion; Ni2+
occupies the octahedral sites and disperses finely with the
Mo06+ promoting better active sites for hydrogenation
activity. CO-MO is generally preferred for HDS activity;
Ni-Mo for HDN and hydrogen uptake in processing
unsaturated fuels. However, Ni-Mo catalysts have substantial HDS activity and may be preferred for HDS when
the feedstock contains substantial products from catalytic
cracking.
Effect of reduction period on catalyst activity

Co-MO/alumina supported catalyst was reduced by

hydrogen gas flow at 210 kPa in a U-type quartz reactor
tube. The effect of reduction time was investigated and the
experimental data are presented in Table 3.
Removal of sulfur content is significant for the catalysts
that have been reduced for 4 h. This time was needed in
order to promote fully reduction of the transition metal
oxide by hydrogen. The activity was more effective for
pretreatment of more than 4 h. Results indicate that nitrogen
and sulfur were adsorbed at different active sites on the
catalyst. Different reduction times were expected to activate
the catalyst sites at different layers.
Viscosity reduction is significant at lower reduction
time. WC atomic ratio indicated the degree of hydrogenation of aromatic is increased by increasing the
pretreatment time. The increment trend was similar to
nitrogen removal. At longer treatment time, heavier
compounds (b.p. > 250C) were cracked to produce lower
boiling point product.
Effect of reaction time on hydrogenation reaction

Reaction time is important for the hydrogenation reaction

carried out in the batch reactor, affecting the reaction
severity. Dispersed Ni-Mo catalyst performance is significantly effected by the reaction time. Pretreated catalysts
showing gradual changes in removal rate are more active at
longer reaction time. The effect on HDN is more significant
compared to HDS. Dispersed Ni-Mo catalyst increased the
WC ratio with reaction time. The increment was significant
at lower reaction time, levelling off after that period. The
effect of presulfided catalyst was steeper than with reduced
catalyst which indicated that better conversion could be
achieved by increasing the reaction time at a constant
temperature.

Catalytic

CONCLUSIONS

Co-Mo/A1203
catalysts were found more
active than other catalysts in upgrading low sulfur
waxy residue in a batch reactor at 340C and hydrogen
pressure of 7 MPa. In the presence of presulfided CoMo/A1203, the product conversion to the lower boiling
point fraction ( < 170C) was 10.8 vol%, HDS of
42.4% and HDN of 72%. The H/C ratio increment
was 30.9% and viscosity reduction 64%.
(2) Water dispersed Ni-Mo catalyst was also effective and
compared favourably with the presulfided supported commercial catalyst. It was more favourable in HDN at any
reaction time compared to CO-MO supported catalyst.
(3) Reduction time was important for reduced CO-MO/
A1203 catalyst in heteroatom removal activity. The
effect on HDN and hydrogenation
activity was more
favourable by the catalyst that had undergone longer
pretreatment time.
(4) Reaction time was a less important factor by itself in the
activity of supported catalyst. The reaction time effect
was more significant in water dispersed catalyst activity. Longer reaction time gave better performance by
the dispersed Ni-Mo catalyst.

of petroleum

residual

oil: K. P. Tian et al.

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ACKNOWLEDGEMENTS

15

Residual oil supply by Petronas Refinery, Melaka and

catalyst sample provided by Professor V. K. Mathur of
University of New Hampshire are gratefully acknowledged.
The authors are grateful to the Universiti &ins Malaysia,
Penang for the financial support for this research work.

16
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Fuel 1998 Volume

77 Number

11

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