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
77 Number
11
1221
Table 1
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
77 Number
range (C)
1222
1
1210
11
Catalytic upgrading
chedcvalve
of petroleum
gasproduct
exhaust
Needle valve
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
160
155
120
170
4.9
10.8
15.1
16.7
14.2
32.5
31.6
20
17
32.4
29.9
(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
77 Number
11
1223
1.95
1.85
Experimental design
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
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
Catalytic
tNi-Mo@ispersed)
+Co-Mo(sulfidcd)
0.4 I
upgrading
of petroleum
residual
oil: K. P. Tian
et al.
Reactiontime (hr).
Figure 3
Ni-Mo (Dispersed)
+-Co-MO
(slllfidcd)
Figure
77 Number
11
1225
W% Naphtha
0% let Fuel
??
% Diesel
W%Gasoil
CO-MO
(sulfided)
Ni-Mo
(Dispersed)
Catalyst type
Figure 5
Table 3
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
1226
77 Number 11
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
REFERENCES
1
(1) Presulfided
upgrading
2
3
4
5
6
7
8
9
10
11
12
13
14
ACKNOWLEDGEMENTS
15
16
17
18
77 Number
11
I227