Conference06-21Nippon Ketjen Resid HDM

40 Years Contribution to
Sustainable Petroleum Refining
The pursuit of efficiency in

Resid HT operation based on
investigation of feed properties
and use of newly developed
KFR catalysts
At 2011 J-C-K Petroleum
Technology Congress
Feb 22-23, 2011
Nippon Ketjen Co., Ltd.
Contents
1. Introduction
2. Reactivity of VR and heavy AR feedstock
3. Introduction of newly developed KFR catalysts
4. Conclusion
1. Introduction
Issues related to Resid hydrotreating are as follows.

- Decrease of demand for fuel oil
- Crude oil is becoming heavier and more diverse
- Treatment of non-conventional crude oil will be
needed
To cope with the above issues, we present the following.
- Investigation of a number of feed properties and their
impact on HDS reactivity
- Newly developed catalysts for a more efficient
operation
40 Years
Years Contribution
Contribution to
to
40
Sustainable Petroleum
Petroleum Refining
Refining
Sustainable
2. Reactivity of VR and heavy AR feedstock
Objectives
Evaluate HDS reactivity for 10 types of different oils

(VR, AR, DAO)
Investigate the relation between HDS activity and feed
properties
Comparison of reactivity under high pressure18MPa and
medium pressure14MPa
Investigate the relation between HDS reactivity and the
molecular structure of the n-C7 insoluble fraction
Specify convenient feed properties that can be used for
selecting crude source and adjusting operation conditions
5
Catalyst system and conditions
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
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
HDS reactivity under high pressure

(18MPa)
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
HDS reactivity under high pressure

(18MPa)
+20
+10
+30
AR
VR
Base
+0
-10
-20
-30
@18MPa
-40
0.92
Temperature required , oC
+30
AR
VR
+20
+10
+0
Base
-10
-20
-30
@18MPa
-40
0.94
0.96 0.98 1.00 1.02 1.04

Density of feed , g/ml at 15oC
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.
Effect of pressure
+30
18MPa
+20
+30
+10
Base
+0
-10
-20
-30
-40
+20
14MPa
+10
Base
+0
-10
-20
DAO
-30
-40
3
4
3
4
5
The influence of pressure on HDS reactivity were evaluated under high

pressure (18MPa) and low pressure (14MPa).
10
Effect of pressure
+30
14MPa
18MPa
+20
+10
Ref.
Base
+0
-10
-20
DAO
-30
-40
1
3
4
5
The difference in HDS reactivity between a certain oil and reference

feed was almost independent of pressure.
11
Factors to affect HDS reactivity
Comparison of feed reactivity from the following

perspective:
- Feeds of markedly different reactivity, but with similar
sulfur content
After separation by n-C7 solubility, the insoluble fraction
Asphaltene and soluble fraction (Maltene) were
investigated individually for their
- HDS conversion
- Averaged molecular structure
Feed or Product oil
Separation by heptane
Soluble
Maltene
Insoluble
Asphaltene
12
Feeds with similar S content
+30
14MPa
18MPa
+20
+10
+0
-10
-20
-30
-40
1
3
4
5
13
Years Contribution to
Comparison of high S vs low S feed 40
2.0
3.0
+20
Sulfur content, wt%
14MPa
18MPa
+10
Base
+0
-10
Sulfur from MAL

Sulfur from ASP
2.5
1.5
1.0
0.5
0.0
Feed
-20
-30
Sulfur in DSAR Sulfur in DSAR

=0.5wt%
=0.3wt%
3.0
2.0
-40
1
Sulfur content, wt%
+30
1.5
2.5
3
4
51.0
Comparing several types of feeds with

similar sulfur content, the less reactive
feeds contain higher amounts of sulfur
in the Asphaltene fraction.
Sulfur from MAL

Sulfur from ASP
0.5
0.0
Feed
Sulfur in DSAR Sulfur in DSAR

=0.5wt%
=0.3wt%
14
Typical molecular structure of

Asphaltenes
+30
14MPa
18MPa
+20
+10
Base
+0
-10
-20
-30
-40
1
3
4
5
15
Typical molecular structure of

Asphaltenes
+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
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
Estimation of reactivity
from analyses
30
0.5
fa, -
0.4
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
Reactivity of VR and heavy AR
The HDS reactivity of the feed correlates relatively strongly

with sulfur content, metals content, specific gravity, CCR
content and Loglog Visof the feed
The HDS reactivity difference between a certain oil and the
reference feed is almost independent of pressure (18MPa or
14MPa)
Higher sulfur removal requires removing the S from
Asphaltenes. The HDS reactivity is affected either by the
feed aromaticity factor or by how bulky the feed Asphaltene
molecules are
The amount of saturates can be used to determine the HDS
reactivity of the feed.
18
3. Introduction of newly developed KFR grades

3.1 New HDM catalyst, KFR 15
3.2 New HDS catalyst, KFR 93
3.3 KFR grades
3.4 Simulated performance of a system using KFR 15
and KFR 93
19
3.1 Introduction of new HDM
catalyst KFR 15
New support technology enabled optimization of pore

structure with higher pore volume
-Improved diffusivity of metal-containing large molecules
-Improved metal capture capability
Optimized surface activity
-Effective to suppress dehydrogenation reaction at
relatively higher reaction temperature after middle of run
20
HDM performance of KFR15

140
130
HDM RVA
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
Metal on Catalyst, g/100ml Catalyst
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
3.2 Introduction of new HDS
catalyst KFR 93
With using commercially proven support technology, both

type of active metals and their metal loadings were
optimized.
We commercialized a high HDS activity
catalyst, KFR 93, which outperforms all currently available
commercial HDS catalysts.
KFR 93 exhibits unparalleled HDS activity in case the
HDM section can satisfactorily reduce metals to the HDS
section.
22
Normalized WAT for HDS, C
HDS performance of KFR 93

+40
420
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
KFR 93 exhibited over 10 oC HDS advantage over KFR 70 with equivalent

stability.
23
3.3 KFR grades
Guard
Catalysts
HDM
Catalysts
KG 55
Ring shaped catalyst, Capture large-size scale
KF 542
Macaroni-shaped ring catalyst, Capture middle-size scale
KG 1
Ball shaped porus catalyst, Capture fine scale and iron
KG 5
Quadralobe catalyst with HDM, For size-grading
KFR 12
HDM catalyst, mainly for low-mid pressure 15MPa , with higher

coke resistance based on KFR 20
KFR 20
High HDM activity catalyst with HDS function, mainly for low-mid
pressure 15MPa
KFR 15
Newly developed HDM catalyst, mainly for high pressure

15MPa, with improved metal tolerance and coke resistance from
KFR 22/23
KFR 23
HDM catalyst, mainly for high pressure 15MPa , with higher

metal resistance based on KFR 22
KFR 22
High HDM activity catalyst with HDS function, mainly for high
pressure 15MPa
24
3.3 KFR grades

HDM/HDS
Catalysts
HDS
Catalysts
KFR 33
Transtion catalyst of HDM and HDS functions, with relatively high

metal tolerance
KFR 53
HDS catalyst with relatively high metal tolerance
KFR 50
High HDS and HDN activity catalyst
KFR 50S
Improved KFR 50 with higher HDS, HDN and HDCCR activity
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
Finishing catalyst with extremely high HDS, HDN and HDCCR

activity
Since the first commercial introduction in 1987, KFR catalysts have been
employed in 26 units with over 100 runs World Wide.
25
Schematic display of KFR activity
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
3.4 Simulated performance of
a new system with KFR 15 and KFR 93
Performance of a new system with KFR 15 and KFR 93 was simulated,

and was compared with current KFR 23/22 and KFR 70.
Catalyst system
System A
Reference System
HDM
KFR 23
KFR 22
Transition
KFR 33
HDS
KFR 70
System B
New System
KFR 15
Replace KFR 23/22 by

KFR 15
KFR 33
KFR 70
KFR 93
Replace latter half of

KFR 70 by KFR 93
27
Performance of new system
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
Days on Stream, day
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
Ni+V Content, ppm
Performance of new system

10
8
6
4
System-A
System-B(New)
0
0
50
100
150
200
250
300
350
Days on Stream, day
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
HDS reactivity of feedstock are related to the molecular

structure of Asphaltenes. More bulky structure and higher
aromaticity leads to less reactivity of the feed. The amount of
saturates can indicate HDS reactivity of the feed.
We commercialized a new HDM catalyst KFR 15 and a new
HDS catalyst KFR 93. Employing these catalysts, the
required temperature for operation can be lowered, or
alternatively, the product metals can be reduced at constant
product sulfur.
Nippon Ketjen is committed to providing optimal catalyst
systems to its customers.
30

Conference06-21Nippon Ketjen Resid HDM

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40 Years Contribution to

Sustainable Petroleum Refining

The pursuit of efficiency in

Nippon Ketjen Co., Ltd.

Issues related to Resid hydrotreating are as follows.

2. Reactivity of VR and heavy AR feedstock

Evaluate HDS reactivity for 10 types of different oils

Catalyst system and conditions

HDS reactivity under high pressure

HDS reactivity under high pressure

0.96 0.98 1.00 1.02 1.04

The influence of pressure on HDS reactivity were evaluated under high

The difference in HDS reactivity between a certain oil and reference

Factors to affect HDS reactivity

Comparison of feed reactivity from the following

Feeds with similar S content

Sulfur content, wt%

Sulfur from MAL

Sulfur in DSAR Sulfur in DSAR

Sulfur content, wt%

Comparing several types of feeds with

Sulfur from MAL

Sulfur in DSAR Sulfur in DSAR

Typical molecular structure of

Typical molecular structure of

Reactivity of VR and heavy AR

The HDS reactivity of the feed correlates relatively strongly

3. Introduction of newly developed KFR grades

New support technology enabled optimization of pore

HDM performance of KFR15

Metal on Catalyst, g/100ml Catalyst

With using commercially proven support technology, both

Normalized WAT for HDS, C

HDS performance of KFR 93

KFR 93 exhibited over 10 oC HDS advantage over KFR 70 with equivalent

3.3 KFR grades

Ring shaped catalyst, Capture large-size scale

Macaroni-shaped ring catalyst, Capture middle-size scale

Ball shaped porus catalyst, Capture fine scale and iron

Quadralobe catalyst with HDM, For size-grading

HDM catalyst, mainly for low-mid pressure 15MPa , with higher

Newly developed HDM catalyst, mainly for high pressure

HDM catalyst, mainly for high pressure 15MPa , with higher

3.3 KFR grades

Transtion catalyst of HDM and HDS functions, with relatively high

HDS catalyst with relatively high metal tolerance

High HDS and HDN activity catalyst

Improved KFR 50 with higher HDS, HDN and HDCCR activity

Finishing catalyst with extremely high HDS, HDN and HDCCR

Schematic display of KFR activity

Performance of a new system with KFR 15 and KFR 93 was simulated,

Replace KFR 23/22 by

Replace latter half of

Performance of new system

Days on Stream, day

Ni+V Content, ppm

Performance of new system

Days on Stream, day

HDS reactivity of feedstock are related to the molecular

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