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Contents
40 Years Contribution to
Sustainable Petroleum Refining
1. Introduction
2. Reactivity of VR and heavy AR feedstock
3. Introduction of newly developed KFR catalysts
4. Conclusion
1. Introduction
40 Years Contribution to
Sustainable Petroleum Refining
40 Years
Years Contribution
Contribution to
to
40
Sustainable Petroleum
Petroleum Refining
Refining
Sustainable
Objectives
40 Years Contribution to
Sustainable Petroleum Refining
40 Years Contribution to
Sustainable Petroleum Refining
Catalyst system
HDM zone KFR 23/KFR 22/KFR 20
HDS zone
KFR 53/KFR 50/KFR 70
Pilot test conditions
ppH2 : 14MPa 18MPa
H2/Oil : 1000NL/L
LHSV : 0.2h-1
Operation target
Product Sulfur 0.3wt% and 0.5wt% in
DSAR(360oC+)
6
Feedstock
40 Years Contribution to
Sustainable Petroleum Refining
VR 10 types
Origin Iranian Light, Upper Zakum, Qatar Marine,
Canadian Heavy, Maya/Isthmus, North Sea main
AR 8 types
Origin: Arabian Heavy, Arabian Extra Light,
Kuwait main
DAO 1 type
40 Years Contribution to
Sustainable Petroleum Refining
Temperature required , C
+30
AR
VR
+20
+10
Base
+0
-10
-20
-30
@18MPa
@18MPa
-40
1
3
4
Sulfur in feed , wt%
In general, the higher the sulfur content in the feedstock, the higher the
required reaction temperature for HDS. The magnitude of the increase
for VR is different from that for AR.
8
+30
AR
VR
Base
+0
-10
-20
-30
@18MPa
-40
0.92
Temperature required , oC
Temperature required , C
+30
40 Years Contribution to
Sustainable Petroleum Refining
AR
VR
+20
+10
+0
Base
-10
-20
-30
@18MPa
-40
0.94
1.06
10
15
20
CCR in feed , wt%
25
30
The HDS reactivity of the feed correlates relatively strongly with specific
gravity, CCR content, metal content and Loglog Vis.of the feed.
40 Years Contribution to
Sustainable Petroleum Refining
Effect of pressure
+30
18MPa
+20
Temperature required , C
Temperature required , C
+30
+10
Base
+0
-10
-20
-30
-40
+20
14MPa
+10
Base
+0
-10
-20
DAO
-30
-40
3
4
Sulfur in feed , wt%
3
4
5
Sulfur in feed , wt%
10
40 Years Contribution to
Sustainable Petroleum Refining
Effect of pressure
Temperature required , oC
+30
14MPa
18MPa
+20
+10
Ref.
Base
+0
-10
-20
DAO
-30
-40
1
3
4
5
Sulfur in feed , wt%
40 Years Contribution to
Sustainable Petroleum Refining
Insoluble
Asphaltene
12
40 Years Contribution to
Sustainable Petroleum Refining
Temperature required , oC
+30
14MPa
18MPa
+20
+10
+0
-10
-20
-30
-40
1
3
4
5
Sulfur in feed , wt%
13
Years Contribution to
Comparison of high S vs low S feed 40
Sustainable Petroleum Refining
2.0
3.0
+20
14MPa
18MPa
+10
Base
+0
-10
2.5
1.5
1.0
0.5
0.0
Feed
-20
-30
3.0
2.0
-40
1
Temperature required , oC
+30
1.5
2.5
3
4
51.0
Sulfur in feed , wt%
0.5
0.0
Feed
14
40 Years Contribution to
+30
14MPa
18MPa
+20
+10
Base
+0
-10
-20
-30
-40
1
3
4
5
Sulfur in feed , wt%
15
40 Years Contribution to
+30
14MPa
18MPa
+20
+10
N
OH
C 10H21
High fa
+0
-10
S
-20
-30
OH
Low fa
-40
1
3
4
5
6
7
Sulfur in feed , wt%
Comparing several types of feeds of similar sulfur content, HDS reactivity
differed with the aromaticity factor of the Asphaltene molecule (fa). A higher
aromaticity factor resulted in a lower reactivity feed.
16
40 Years Contribution to
Sustainable Petroleum Refining
Estimation of reactivity
from analyses
30
0.5
fa, -
0.4
Temperature required , oC
14MPa
18MPa
0.3
0.2
0.1
0
AR
VR
20
10
Base
0
-10
-20
-30
-40
10
15
20
Saturate in feed , wt%
25
30
10
15
20
Saturate in feed , wt%
25
30
The aromaticity factors fa has a clear correlation with the amount of saturates.
The HDS reactivity has a strong correlation with the amount of saturates.
The amount of saturates can be measured easily and it can be used to
determine the HDS reactivity of the feed.
17
40 Years Contribution to
Sustainable Petroleum Refining
40 Years Contribution to
Sustainable Petroleum Refining
40 Years Contribution to
3.1 Introduction of new HDM
Sustainable Petroleum Refining
catalyst KFR 15
20
40 Years Contribution to
Sustainable Petroleum Refining
Test Conditions:
Temp. , oC
360 - 405
ppH2
, MPa
18
H2/Oil , NL/L
800
-1
LHSV , h
1.0 - 3.0
Feedstock Properties:
Sulfur , wt%
4.1
Ni+V
, ppm
100
3
Density , g/cm
0.977
KFR 23
KFR 15
120
110
100
90
80
0
10
20
30
KFR 15 shows higher HDM performance than KFR 23 from start of run.
With its higher metals pickup capacity the catalyst however showed an
even more prominent advantage after middle of run.
21
40 Years Contribution to
3.2 Introduction of new HDS
Sustainable Petroleum Refining
catalyst KFR 93
22
40 Years Contribution to
Sustainable Petroleum Refining
Test Conditions :
ppH2, MPa
410
+20
400
390
Base
380
370
-20
360
KFR 70
350
KFR 93
17
0.32
0.3
LHSV, h-1
Target Sulfur, wt%
Feedstock Properties :
Demet. Feed of AR/VR=70/30vol%
Sulfur, wt%
1.4
Ni+V, ppm
18
-40
340
0
50
50
100
100
150
150
200
250
250
300
300
Days on
Days
onstream
stream
Guard
Catalysts
HDM
Catalysts
40 Years Contribution to
Sustainable Petroleum Refining
KG 55
KF 542
KG 1
KG 5
KFR 12
KFR 20
High HDM activity catalyst with HDS function, mainly for low-mid
pressure 15MPa
KFR 15
KFR 23
KFR 22
High HDM activity catalyst with HDS function, mainly for high
pressure 15MPa
24
HDS
Catalysts
40 Years Contribution to
Sustainable Petroleum Refining
KFR 33
KFR 53
KFR 50
KFR 50S
KFR 70
Finishing catalyst with very high HDS, HDN and HDCCR activity
KFR 70B/71B
Improved KFR 70 with higher HDS, HDN and HDCCR for paraffinic
AR
KFR 93
Since the first commercial introduction in 1987, KFR catalysts have been
employed in 26 units with over 100 runs World Wide.
25
40 Years Contribution to
Sustainable Petroleum Refining
Metal Capacity
KFR 15
KFR 23
KFR 22
KFR 12
KFR 20
KFR 33
KFR 53
KFR 50
KFR
KFR 70
KFR 50S
KFR 70B/71
93
HDS Activity
Only the sophisticated combination of high performance catalysts can fully meet a
unit requirement.
We are now expanding our versatile and balanced HDM/HDS system by further
improvement of the HDM activity/metal tolerance with KFR 15 and by adding
extremely high HDS activity with KFR 93.
26
40 Years Contribution to
3.4 Simulated performance of
Sustainable Petroleum Refining
a new system with KFR 15 and KFR 93
KFR 23
KFR 22
Transition
KFR 33
HDS
KFR 70
System B
New System
KFR 15
KFR 33
KFR 70
KFR 93
27
40 Years Contribution to
Sustainable Petroleum Refining
Feedstock Properties :
Sulfur,
wt%
Ni+V,
ppm
3
Density,
g/cm
0.15
18
0.3
4.4
95
0.995
Operation WAT, C
Operation Conditions :
-1
LHSV,
h
ppH2,
MPa
Target Sulfur,
wt%
20
+20
15
10
+10
5
System-A
0
Base
System-B(New)
-5
-10
-10
0
50
100
150
200
250
300
350
Simulation indicated that the new system B with KFR 15 and KFR 93 can
lower around 2oC of WAT after MOR compared to system A.
28
40 Years Contribution to
Sustainable Petroleum Refining
System-A
System-B(New)
0
0
50
100
150
200
250
300
350
The new system B with KFR 15 and KFR 93 can reduce metals in product
from 6 to 4ppm at SOR and 9 to 7ppm at EOR, and the difference of metal
content between system A and B is 2ppm through the run at constant product
sulfur. It is expected that system B can reduce FCC catalyst consumption by
70-80% of system A.
29
4. Conclusion
40 Years Contribution to
Sustainable Petroleum Refining
30