A comparison

of alumina,
carbon and
carbon-covered
alumina as supports
for
Ni-MO-F
additives:
gas oil
hydroprocessing
studies
P. Michael
Jenny
M.

Boorman,
Lewis and

Department
of Chemistry,
( Received 5 April 7997 )

Ronald
Wesley
University

A. Kydd,
S. Bell

Ted S. Sorensen,

of Calgary,

Calgary,

Alberta,

Kenneth
Canada

Chong,

T2N

lN4

Catalysts with 3 wt% NiO. 15 wt% MOO, and O-6.9 nominal wt% fluoride supported on alumina, carbon
and carbon-covered
alumina were studied to examine the role of fluoride and the influence of the support
on hydroprocessing
on Alberta gas oil. Experiments
were carried out in a batch reactor at 410 C and
6.9 MPa initial H, pressure. It was found that fluoride promotion
enhances cracking and hydrogenation
reactions resulting in decreased aromatic and sulphur contents in the gas oil. The promotion is dependent
on the type of support and is related to the strength of the fluoride-support
interaction and the accessibility
of the fluoride to the surface hydroxyl groups on the support. A maximum in activity at 3.6 wt% fluoride
was observed for the alumina-supported
catalysts whereas higher loadings of fluoride were required for
carbon-covered
alumina-supported
catalysts
to see an improvement
over their carbon
supported
counterparts.
However, the carbon-covered
alumina supported catalysts seem to have a lower propensity
for coke deposition than their alumina counterparts.
(Keywords:

carbon; gas oil; hydroprocessing)

Synthetic
crude oil derived from the Athabasca
oil sands
deposit
and upgraded
currently
accounts
for well over
10 ~01% of Canadas
crude
oil production.
In these

operations,
synthetic crude oil is produced by upgrading
the bitumen
using delayed
coking
or fluid coking
combined with hydrocracking.
The liquid products from
the primary
upgrading
are classified
into naphtha
(82- 177 C), middle distillate ( 1777343 C ) and gas oil
(3433525 C) fractions
which subsequently
must be
refined. The naphtha cut can undergo catalytic reforming
to produce gasoline, the middle distillate cut can be used
to produce aviation
and diesel fuel, and the gas oil
fraction can be further processed
in a fluid-catalytic
cracker. However, with regard to the middle distillates,
the current situation in Canada is one in which refineries
have only a limited capability
to process the synthetic
crude feedstocks
with a conventional
refinery being
restricted
to an intake of synthetic
crude up to a
maximum
of I5 ~01%. This is because the synthetic
crude middle distillate cut has too high an aromatics
content and too low a cetane number to meet current
specifications for jet fuel and diesel fuel, respectively. The
demand
for these middle
distillate
fuels and the
production
of synthetic
crude relative
to oil from
conventional
oil reserves
is projected
to increase4.
Because of these facts, coupled
with the possible
implementation
of more stringent
specifications
for sulphur

and aromatics,
alternative
or additional
processing
methodologies
will be needed eventually
to replace
the current
practice of blending
synthetic
with conventional crudes to accommodate
refinery operations.
Some processing
alternatives
have recently
been

0016-2361.92,!01008747
c 1992 Butterworth-Heinemann

Ltd.

reviewed3. Most technologies

available at the present
time utilize catalysts with metals such as Pt or Ni, or Ni
in conjunction
with MO or W supported on alumina..
The aims of the present study are two-fold;
first, to
investigate the role of fluoride, a promoter;
and second,
to investigate
alternative
support
materials,
namely
carbon
and carbon-covered
alumina,
and ascertain
whether
they may prove viable in hydroprocessing
applications.
In recent years, there has been growing interest in using
carbon materials as catalyst supports. Reduced coking
propensity,
easy metals recovery from spent catalysts*
and improved thiophene hydrodesulphurization
conversions for carbon supported catalysts are the reported
advantages over their alumina counterparts.
It should be
noted that studies have not been limited to model
compounds.
Several researchers have reported promising
results when using carbon supported
catalysts for real
feedstocks such as coal-derived
liquids12, bitumen
and
a coallheavy
oil mixture in a coprocessing application3.
However, there are some reservations
about the use of
carbon
materials
as supports
for hydroprocessing
applications.
Much of the surface area may be in very
small pores, and such supports have poor mechanical
properties,
disadvantages
not discerned
for alumina ;
these may limit its utility as a support. Thus an ideal
support may result by merging the attributes
of both
support systems. Coating the alumina surface with a thin
layer of carbon
may result in a support
with the
fdvourable physical properties of alumina while imparting reduced coking propensity.
Sulphided Co catalysts
supported on carbon-covered
alumina were reported to

FUEL,

1992,

Vol 71, January

87

Gas oil hydroprocessing

studies:

et al

P. M. Boorman

have a thiophene hydrodesulphurization

activity between
those of their carbon
and alumina
counterparts14.
Cumene and thiophene model compound
reactions over
fluorided Ni-Mo catalysts supported on alumina, carbon
and carbon-covered
alumina have been studied and it
was found that a carbon-covered
alumina surface exhibits
the catalytic
properties
of both support
materials
promoting hydrogenation-dehydrogenation
reactions as
a result of the deposited
carbon,
and hydrocracking
reactions due to the fluorided alumina
surface.
The
influence of fluoride, which polarizes the alumina lattice
thereby increasing
the BrBnsted acidity and enhancing
the cracking ability, has been demonstrated
previously
in model compound6-18
and real feedstock
studies.
The use of fluorided carbon-covered
alumina as a support
for real feedstocks, therefore, may give a multi-faceted
catalyst with an improved
capability
to hydrogenate
aromatics
while retaining
the enhanced
hydrocracking
ability imparted by the addition of fluoride to alumina.
This study extends previous work and explores the
role of the support
and fluoride promotion
in the
hydrotreating
of a real feedstock,
namely
Syncrude
combined
gas oil (182-525C).
Three
series
of
fluoride-promoted
Ni-Mo
catalysts
supported
on
alumina,
carbon
and carbon-covered
alumina
were
evaluated for their sulphur removal, hydrocracking
and
hydrogenating
capability in the hydroprocessing
of this
feed. The spent catalysts were also characterized
to give
an insight into the deactivation
properties of the catalyst.
These results are compared with those obtained in the
previous study using model compounds.

Table 1

Properties

of Syncrude

Density (gcmm3 at 16C)

Sulphur (wt%)
Aromatic carbon by 13C n.m.r.
H :C ratio
Distillation
(ASTM D2887)
Initial b.p. (C)
IBP-343C (~01%)
343Cf
(vol%)

combined

EXPERIMENTAL
Muterials

The Syncrude combined gas oil was supplied by the

Alberta Research Council. Its properties are described in
Tuhle 1. The method used to prepare the catalysts has
been described in detail elsewhere15. Briefly, the supports
were impregnated
with the additives
dissolved
in a
minimum volume of distilled water to give 3 wt% NiO,
15 wt% MOO, and various nominal fluoride concentrations. (NH,),Mo,O,,
.4H,O,
Ni(NO,),.6H,O
and
NH,F
were used as sources of MO, Ni and fluoride,
respectively.
The catalysts were dried in air at room
temperature
overnight
followed by drying at 100C
overnight. The alumina supported catalysts were calcined
by heating at 4C min- to 500C and maintaining
this
temperature
for 4 h under a stream of air. The carbon
and carbon-covered
alumina catalysts were not calcined
because oxidative degradation
would occur.
The preparation
of the ;I-alumina
support has been
described previously . The activated carbon was used
as supplied, following drying at 100C for 24 h. The
preparation
of the carbon-covered
alumina followed a
similar procedure to that used by Vissers et a1.14 involving
pyrolysing cyclohexene at 600C. Approximately
3 g of
y-alumina were placed in a calcination
tube and heated
to 600C at a rate of 10C min-
a dry N, flow of
20 ml min-. It was held at 600C for 30 min after which
time the N, was bubbled through cyclohexene,
held at
room temperature,
before passing over the alumina for
6 h at 600C. The sample was allowed to cool under a
flow of dry N,. The pore volumes were 0.65, 0.60 and
2.30 ml g- for the alumina, carbon-covered
alumina and
carbon
supports,
respectively.
Table
2 gives the
designations,
compositions
and surface areas of the three
catalyst series. A more complete description of the carbon
deposition characteristics
(including changes in the pore
size distribution)
and the methods used to determine the
surface area and fluoride content of the catalysts are
discussed elsewhere15. The spent catalysts were characterized after washing with 10 ml of CH,Cl, and drying.

gas oil
0.9917
4.79
37
1.40

(%)

182
29.4
70.6

Gas oil lzydroprocessiny

Experiments

Table 2

Composition

and surface

procedure

were carried

out in a 300 ml Hastalloy

areas of catalysts
Additives

(wt%

Support

Catalyst

NiO

MOO,

F nom

F,,,S.

y-Al,O,

Al
A2
A3
A4
A5

0
3
3
3
3

0
15
15
15
15

0
0
1.8
3.6
6.9

CA1
CA2
CA3
CA4
CA5

0
3
3
3
3

0
15
15
15
15

0
0

Cl
c2
c3
c4
c5

0
3
3
3
3

0
15
15
15
15

0
0

1.8

1.2
2.3
4.9

C/AI,O,

Carbon

The carbon-covered

88

FUEL,

1992,

alumina

catalysts

have 1 I

Vol 71, January

wt% carbon coverage

I .8
3.6
6.9

3.6
6.9

1.8
3.5
6.4
_

I .4
2.3
5.7

Surface area
(mZgm)
190
137
125
122
113
153
109
97
91
91
1357
599
567
652
600

Gas oil hydroprocessing

batch reactor. Each experiment consisted of three stages.

First, 1 g of catalyst sieved to ~425 pm was sulphided
by 2 ml of CS, under 6.9 MPa (1000 psi) initial H,
pressure at 440C for 3 h (including
- 1 h to reach
440C). The sulphided catalyst was then cooled to room
temperature
and all gases vented from the system.
Second, removal
of excess sulphur
was effected by
re-pressurizing
to 6.9 MPa with H, under the same
conditions as for sulphiding. Finally, the hydroprocessing
experiment was carried out by adding 22 + 0.5 g of gas
oil under positive Ar pressure to prevent the catalyst from
being exposed to air. The system was then pressurized
to 6.9 k 0.35 MPa (1000 + 50 psi) with H, at room
temperature.
The reaction
was continuously
stirred
during the experiment
and was maintained
at -410C
for 3 h. The H, pressure was not maintained
at a constant
value during the course of the reaction. After this time
the reactor was cooled rapidly to room temperature.
The
reactor was computer controlled
and a combination
of
the reactor furnace and cooling coils in the reactor were
used to maintain
constant
temperature.
The typical
temperature
range during a reaction was 408 i 3C.

The hydroprocessed
gas oil was analysed to evaluate
the catalysts
ability
to hydrogenate,
crack larger
molecules into smaller ones and remove sulphur. The
carbon and hydrogen
contents
were determined
and
sulphur was analysed by X-ray fluorescence. The densities
at 16 C and viscosities at 25C were determined
using a
density
meter and a viscometer,
respectively.
The
aromatic content of the products was determined by 3C
n.m.r. using an inverse gated decoupling pulse sequence
and a long inter-pulse delay of 20 s. A shorter delay time
of 1 s with Cr( acac), as a relaxation agent was also used.
Comparable
results were obtained for both methods. The
solvent was CDCl,. The percentage aromatic carbon was
determined
from the integrated
aromatic and aliphatic
regions.

RESULTS

AND

DISCUSSION

The catalyst compositions

and surface areas are listed
in Tab/e 2. The carbon-covered
alumina
had 11 wt%
carbon. This is consistent with the reported coverage and
with previous observations,
where it was established
that the deposited carbon results in a lowering of surface
area. This was reproduced
in this work and it may be
concluded
that under these deposition
conditions,
the
carbon clearly is not being deposited in a form with the
pore structure development
like that of the pure carbon
support, which would give rise to an increase in surface
area. Instead, at this level of coverage, the carbon is more
likely being deposited
into the pores of the alumina
support
thereby
degrading
the pore structure
and
decreasing the accessible surface area.
The surface area of the carbon support is much larger
than that of alumina
or carbon-covered
alumina.
However, in spite of this, a similar mode of deposition
upon the addition of the metal salts and fluoride onto
the support surfaces can be inferred from the surface area
decreases for all three supports. The addition of the metal
salts results in a large surface area decrease with much
smaller decreases in surface area occurring
with the

studies:

P. M. Boorman

et al.

successive addition
of fluoride. A possible explanation
for this is the preferential deposition of additives into the
smaller pores of the supports.
Thus the larger metal
additives, being added first, exert the greatest influence
on surface area reduction while the smaller fluoride ions
have a less dramatic
effect on these pores which are
plugged to some extent by the metal additives.
Conclusions
about the strength
of the interaction
between fluoride and the support can be made based on
the fluoride
content
(Table 2). The alumina-based
catalysts
retain nearly quantitatively
all the fluoride
deposited, even after calcination.
This is because of the
surface hydroxyl groups of alumina which exchange with
the fluoride resulting in Al-F bond formation
and a
consequential
increase
in Bronsted
acidity2.
Less
fluoride is retained on the carbon-supported
catalysts,
indicative of a much decreased interaction
between the
fluoride and the support. This is more apparent
after
thermal treatment of the catalysts where the majority of
fluoride is lost. The amount
of fluoride retained
on
carbon-covered
alumina is intermediate
to that for the
alumina and carbon-based
catalysts. This suggests that
the deposited carbon covers some of the alumina surface
and thereby limits the accessibility
of fluoride to some
extent. The nature of the fluoride support interaction will
be discussed later.
H~droyen uptake
Tab/e 3 gives the results for gas oil hydroprocessed
with and without a catalyst. A direct measure of the
catalysts ability to facilitate hydrogen
uptake can be
made by observing
the catalysts
influence
on the
hydrogen
to carbon
ratio and percentage
aromatic
carbon of the gas oil.
Treating
the gas oil without a catalyst under the
conditions
used for the present experiments
(41OC,
6.9 MPa initial H, pressure, 3 h) indicates that hydrogen
uptake
by thermal
processes
is occurring.
This is
evidenced by the increased hydrogen to carbon ratio and
reduction in percentage aromatic carbon from 37 to 34%.
In contrast, Khorasheh
et al. reported an increase in
aromaticity
under thermal hydrocracking
conditions
for
a continuously
stirred flow reactor at similar temperature
and pressure
(LHSV - 1 ml (h ml)- , constant
H,
pressure).
The reasons for this may be the following.
Previous
work22 has shown that hydrogenation
of
aromatics depends sensitively on residence time in a flow
reactor that is operating at the reaction temperature
used.
Hence longer residence times in a batch reactor would
be expected to favour hydrogenation.
Furthermore,
it
has been established
that the equilibrium
between the
hydrogenation
of aromatics to naphthenes
is shifted in
favour of aromatics with increasing temperature22.
Thus
if the reaction products in the present study are cooled
more slowly than those of Khorasheh
et al.,
the
equilibrium
may shift to favour hydrogenation
in the
present case.
The supports alone (A 1, CA 1, Cl ), rather surprisingly,
appear to have an inhibitory effect on the hydrogenation
of the feed. The hydrogen uptake is suppressed (lower
hydrogen to carbon ratio) and the percentage aromatic
content increases significantly
above that for the feed.
The generation
of carbocation
centres may be occurring
due to the intrinsic acid sites present on alumina. In the
absence of hydrogenation
(metal) sites, isomerization

FUEL,

1992,

Vol 71, January

89

Gas oil hydroprocessing

Table 3

Properties

studies:

of hydroprocessed

P. n/l. Boorman

et al.

gas oil

Catalyst

H :C

Aromatics

( %I I

Density

(gcmm3)

Viscosity

Sulphur

Noneh

1.47

34

0.9534

13.1

2.24

AI
A2
A3
A4
AS

1.35
I .59
I .56
1.61
1.62

42
25
23
21
25

0.9529
0.9015
0.9034
0.8948
0.9053

8.7
8.6
7.2
7.1
8.0

3.12
0.5 I
0.4 I
0.25
0.40

CA1
CA2
CA3
CA4
CA5

I .45
I .56
1.56
1.55
I .58

40
30
32
29
28

0.9506
0.9198
0.9177
0.9163
0.9103

9.5
9.3
9.3
9.2
x.5

2.78
0.x0
0.73
0.70
0.60

I .32

42
31
32
33
32

0.9484
0.9 I69
0.9194
0.9159
0.9234

10.0
9.9
9.6
IO.1
9.6

3.59
0.74
0.67
0.75
0.90

Cl
C2
c3
c4
c5

I .59
I .58
1.51
1.57

(wit% )

Per cent relative viscosity; untreated gas oil = 100%

Under H, only (thermal hydrocracking)

and condensation
type reactions may occur resulting in
increased aromatic structures. However, it is unlikely that
the carbon has any inherent acidity and therefore it could
not generate carbocation
species. It is possible that the
carbon surface without the presence of metal species may
act as a dehydrogenation
surface opposing
thermal
hydrogenation,
resulting in a decrease in hydrogen
to
carbon ratio and increase in aromatic carbon character.
Another explanation
for these results is that a free radical
chain mechanism is in operation in the absence of catalyst
but upon addition
of the blank supports,
sites arc
provided which facilitate chain termination
reactions.
This seems the more plausible explanation.
especially
since the same effect is observed for all three supports.
The addition of metal salts to all three support systems
(A2, CA2, C2) caused a dramatic improvement
in the
hydrogen uptake capability. The increase in hydrogen to
carbon ratio is comparable
for all three support systems
while the reduction
in aromatic carbon is comparable
for the carbon and carbon-covered
alumina supported
catalysts but the alumina
supported
catalyst shows a
greater reduction
in aromatic
character.
The alumina
support loaded with metal sulphides such as MoSz can
develop
BrQnsted acidity23 and these sites may be
responsible
for the cracking of aromatic structures.
On
the carbon-covered
alumina
there are expected to be
fewer sites of this type and so no such effect is observed.
Knowing
that alumina is capable of generating
acid
sites via its surface hydroxyl groups and that carbon has
insufficient
hydroxyl
functionality
to develop surface
acidity, the effect of fluoride in the enhancement
of acidity
can be rationalized.
From the hydrogen uptake results.
it is clear that the influence of fluoride is closely linked
with the nature of the support.
The carbon support,
which lacks the surface functionality
required for fluoride
to impart
its modifying
effect, does not show any
discernable
trend when fluoride is added. The alumina
supported catalysts are modified by fluoride addition and
the degree of enhancement
depending on the amount of
fluoride
added.
A maximum
in aromatic
carbon
reduction
is observed
at 3.6 wt% fluoride
(A4). A
maximum
is not seen for the carbon-covered
alumina
catalysts. Instead, it appears that the deposited carbon
acts to suppress the influence of fluoride by covering up

90

FUEL, 1992, Vol 71, January

hydroxyl sites resulting in fluoride promotion

only at
higher loadings of fluoride. This suggests that either the
deposited fluoride does not selectively migrate to the
alumina support, or that the fluoride which does interact
with the alumina surface at low loadings is ineffective in
reactions due to the coverage of carbon, i.e. these sites
are accessible to fluoride but not to the larger feed
molecules. Based on the amount of fluoride retained by
the spent catalysts the latter is the more likely scenario.
It appears that fluoride can reduce the aromatic content
of gas oils, a desirable
feature in hydroprocessing
catalysts. The reasons for this may be two-fold. First, a
direct effect of the fluoride on the alumina support giving
Bronsted acid sites resulting in the cracking of aromatic
structures
and second, an indirect
effect where the
fluoride increases
the metal dispersion
on the support 24m26. As the metals
are the active sites for
hydrogenation,
an increased metal dispersion
may be
partly responsible for a reduction in aromatic carbon by
the hydrogenation
of aromatic structures.

The chemical composition

of heavy oil is very complex
consisting primarily of very large molecules with a high
degree of unsaturation.
Thus the objective in hydroprocessing is to crack and hydrogenate
the large molecules
into smaller entities. Typically, cracking and hydrogenation reactions are facilitated by thermal mechanisms
or
by acid catalysts such as metals supported on alumina.
The acid sites can generate carbocation
intermediates
which can then undergo subsequent
rearrangement
and
cleavage reactions while the metal species provide active
hydrogenation
sites. The use of viscosity and density
measurements
provides a probe by which the degree of
cracking and hydrogenation
can be determined
and the
results are presented in Tuhle3.
Thermal treatment
of the gas oil shows a significant
drop in density and viscosity indicating thermal cracking
and hydrogenation
occurs at the 41OC used. The blank
supports possess some inherent cracking ability above
that which is due to thermal cracking,
based on the
density and especially by the viscosity measurements.
This slight improvement
is attributed
to cracking

Gas oil hydroprocessing

1 .oo

.
.

0.80

ri

0.60

+
+

0.40

0.20
20

30

26
%

Aromatic

36

carbon

Figure I Sulphur (wt/,) versus aromatic

carbon (%) for catalysts
containing
3 wt% NiO. 15 wt% MOO, and O-6.9 wth F supported
on: +, alumina;
A, carbon-covered
alumina;
0, carbon

reactions
since the supports alone have an inhibitory
effect on hydrogenation
as previously
described.
On
increasing
the acidity of the catalysts through Ni-Mo
and fluoride addition,
similar trends to those observed
for hydrogen
uptake
are observed
for the reasons
discussed previously. A highlight is the effect of fluoride,
particularly
at 3.6 wt% for the alumina
supported
catalysts. This suggests that cracking and hydrogenation
reactions
for gas oil can be influenced
by fluoride
addition. This could result in lower operating temperatures
and consequently
longer catalyst lifetimes, since less coke
deposition
occurs on the catalyst
surface at lower
temperatures 27. It is interesting to note that these effects
of fluoride, i.e. maximum activity at 3.6 wt% for alumina
and increasing influence with loading for carbon-covered
alumina
are the same as those observed in previous
cumene model compound
reaction studiesI
confirming
the usefulness of model compound studies as an indicator
of catalyst performance when extended to real feedstocks.
What is interesting
to note is the low density of the
feed treated by the carbon supported catalysts. These are
in fact comparable
to the values for the feed when
carbon-covered
alumina catalysts are used. Carbon lacks
the surface acidity required
to mediate
carbocation
cracking
mechanisms,
as demonstrated
in model
compound
studies 5 and, indeed, there is no significant
difference or trend apparent in the density and viscosity
measurements
as the fluoride
concentration
in the
catalyst increases (C2-C5).
Thus this improvement
in
density and viscosity is most likely due to the presence
of metal sites hydrogenating
the feed.
Sulphur

removal

The removal of heteroatoms,

particularly
sulphur, is
necessary before subsequent
refining reactions
can be
undertaken
and to satisfy environmental
concerns. The
results presented indicate that the ability of the catalyst
to facilitate the removal of sulphur from the gas oil is
directly
related
to both
the catalysts
ability
to
hydrogenate
the feed and its ability to facilitate cracking
reactions. Comparing the sulphur removal in the absence
of a catalyst to that in the presence of the supports alone,
an apparent
inhibitory
effect is again seen when the
supports are present. This suggests the blank supports
do not facilitate
sulphur
removal
and that sulphur

studies:

P. A4 Boorman

et al.

removal by thermal mechanisms

is suppressed.
This is
possibly due to the supports generating
hydrocarbon
species which are preferentially
hydrogenated
over
sulphur
containing
molecules
or by the supports
providing sites where the generated free radical species
can undergo termination
reactions.
The need for active sites, i.e. supported metal sulphides,
to facilitate sulphur removal is evident from these results.
Although
there is controversy
concerning
the exact
mechanism
for hydrodesulphurization,
it is clear from
the present results that both the cracking
of larger
molecules into smaller ones and the degree of hydrogen
uptake dictate the amount of sulphur removed. This is
not surprising
as the cracking of larger molecules into
smaller ones would make them more accessible to the
active sites and hydrogenation
of thiophenic
type ring
structures would weaken the C-S bond making it more
susceptible
to bond cleavage.
Figure
I shows the
relationship
between
weight per cent sulphur
and
percentage aromatic carbon. This clearly shows that a
correlation
exists between reduction in aromatic carbon
and lower sulphur levels. The fact that the blank supports
suppress hydrogen uptake and sulphur removal but not
cracking reactions suggests that hydrogenation
may be
the rate determining
step for sulphur removal from gas oil
feedstocks under our reaction conditions.
It appears then for real feedstocks that sulphur removal
is facilitated by cracking and hydrogenation,
and thus a
correlation
should exist between sulphur removal and
the presence
of fluoride
for catalysts
containing
a
hydrogenating
(metal) phase. This is indeed what is
observed:
alumina
catalysts
have the best sulphur
removal capability with a maximum activity at 3.6 wt%
fluoride;
carbon-covered
alumina
catalysts are intermediate in ability and the sulphur removal increases with
increasing
fluoride;
finally,
the carbon
supported
catalysts present no clear trend in activity as the weight
per cent fluoride is increased. Thus by increasing
the
hydrogen uptake and enhancing cracking type reactions,
fluoride acts indirectly to promote sulphur removal. This
is in contrast to the thiophene model compound studies15
in which a decrease in sulphur removal capability
was
observed with increasing
fluoride content for alumina
and carbon-covered
alumina catalysts. However, in the
hydrodesulphurization
of such a small molecule, cracking
is not necessary in order to make the sulphur accessible
to the catalyst surface (as it may well be for the large
feed molecules)
and therefore the influence of fluoride
may not be manifested.
Characterization

qfspent

catalysts

The recovered catalysts were characterized

to give an
insight into the nature of the fluoride interaction
with
the support and deactivation
properties of the catalysts.
The results are presented in Table 4. The fluoride analyses
of the spent catalysts, particularly
the carbon supported
catalysts, are approximate
since the exact weight per cent
of coke is not known. First, from the fluoride analysis
of the spent catalysts, it is evident that the interaction
between fluoride and carbon is much weaker than for
alumina
or carbon-covered
alumina.
Nearly all the
fluoride is lost from the carbon supported catalysts while
on alumina and carbon-covered
alumina, all the fluoride
is retained at lower loadings, and upwards of 75% is
retained at the higher loadings.
The original
11 wt%

FUEL,

1992,

Vol 71, January

91

Gas oil hydroprocessing

Table 4 Composition
Catalyst

studies:

and surface

CA1
CA2
CA3
CA4
CA5
Cl
c2
c3
c4
c5

Fluoride
(wt%)

Carbon
(wt%)

Surface
(mg-I)

1.8
2.9
4.8

8.9
9.2
4.9
6.6
6.4

121
73
82
62
66

I .4
2.3
4.6

6.0
2.8
4.7
8.8
2.3

92
63
39
24
58

0.027
0.076
0.15

This value is per gram

carbon-covered
alumina
present. Carbon-covered
original 11 wt% carbon

et al.

area of spent catalysts

~~.
Al
A2
A3
A4
A5

P. M. Boorman

_
_

area

63
42
_
44

of support, i.e. wt% carbon for alumina and

catalysts for the fluoride and metal sulphides
alumina catalysts are also adjusted for the
present

carbon deposited for the carbon-covered

alumina series
does not limit fluoride from access to the alumina surface.
In fact, the carbon-covered
alumina support seems to
retain fluoride better than alumina.
The amount of deposited carbon on the spent catalysts
and reduction in surface area gives an indication
of the
catalysts susceptibility
to deactivation
by coking. The
weight per cent carbon values quoted in Tuhle 4 have
been corrected for metal sulphides and retained fluoride.
Again
these
numbers
are approximate
since the
heteroatom
content of the coke is not known. However,
some general observations
may be made. First, the
presence of fluoride does not appear to increase the
amount of coke deposited. This is supported by previous
findings
where with pre-coked
alumina
supported
catalysts via cyclohexene pyrolysis it was found that at
least for coke deposition via this method, it was facilitated
by metal additives,
not fluoride.
This led to the
suggestion that Lewis acidity, not BrDnsted acidity, was
an important factor in coking. Second, a promising result
is that in general, the amount of carbon deposited on
carbon-covered
alumina
catalysts
is less than that
deposited on the alumina supported catalysts, especially
at high fluoride loadings. This is consistent with reports
of reduced coking propensity
for carbon
supported
catalysts.
Also, the fact that there is less coke on the
catalysts
with high fluoride
content
supports
the
proposed synergy between cracking by fluorided alumina
and hydrogenation
by the metal phase. Thus carboncovered alumina may successfully merge the properties
of both support systems-fluoride
promotion
at high
fluoride loadings associated with alumina and reduced
coking propensity
associated
with carbon.
It may be
possible
to see a maximum
in activity
for the
carbon-covered
alumina catalysts like that seen for the
alumina supported
catalysts by increasing
the fluoride
loading above that studied in the present work without
increasing the amount of coke deposited on the catalyst
surface and this merits further investigation.
The surface areas of the spent catalysts
decrease
substantially
for the alumina
and carbon-covered
alumina
series under these reaction
conditions,
and

92

FUEL, 1992, Vol 71, January

decrease drastically for the carbon supported catalysts.

Although the amount of coke deposited on carbon may
be no more and possibly less than for alumina supported
catalysts, this result questions the utility of much of the
surface area in carbon which is in very small pores and
consequently
quickly coked.

CONCLUSIONS
1. The addition
of Ni-Mo
and fluoride to alumina,
carbon-covered
alumina
and carbon
increases
the
amount that the feed is hydrogenated
depending on the
Bronsted acidity of the catalysts. The influence of fluoride
on alumina based catalysts is such that a maximum in
activity is observed at 3.6 wt% fluoride with the greatest
decrease in aromatic carbon content. Higher loadings of
fluoride
are required
for carbon-covered
alumina
catalysts
to see an improvement
over their carbon
counterparts.
These trends in activity correlated with a
previous study based on model compounds.
2. By increasing the ability of the catalyst to hydrogenate
the feed and enhancing cracking type reactions, fluoride
acts indirectly to promote sulphur removal.
3. NiO-Moo,-F
(3-15-3.6
wt%) supported
on alumina was the optimum catalyst for hydroprocessing
gas
oil in this study. Fluoride at higher loadings is effective
for carbon-covered
alumina catalysts ; these also exhibit
reduced coking propensity.
Thus, it may be possible to
prepare a superior catalyst based on carbon-covered
alumina with higher fluoride loadings.

ACKNOWLEDGEMENTS
The authors thank the Alberta Research Council for the
gas oil and Alberta Sulphur Research for the use of their
density meter, viscometer
and sulphur analyser.
The
project was funded by the Alberta Oil Sands Technology
and Research Authority (AOSTRA).
KC and JML also
thank AOSTRA for support in the form of graduate
scholarships.
The authors also thank a reviewer for the
helpful suggestions.

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93