11
Advanced Technology Developmentfor Sulfur-free Fuels Production
February 19th 2009
Seiji KasaharaMarifu RefineryNippon Petroleum Refining Company, Ltd. (Nippon Oil Corporation; NOC)
The 7th Asian Petroleum Technology Symposium
22
1. General Information on NOC/NPRC
2. Sulfur Regulations in Japan
3. Technology for Sulfur-free Diesel Fuel
4. Technology for Sulfur-free Gasoline
5. Production Process at Marifu Refinery
6. Conclusions
Agenda
33
General Information on NOC/NPRCGeneral Information on NOC/NPRC
NOC and its affiliate companies have 10 refineriesthroughout Japan, including 2 lubricant manufacturing facilities without CDU
Overall capacity of the refineries is 1,377kB/D,which is equivalent to about 28% of the domestic oil refining capacity in Japan
Company Founded: May 10th 1888
Capital: 139 billion yen
Number of employees: approx. 5,800**NOC & NPRC (Nippon Petroleum Refining Co., Ltd.)
NPRC is NOC‘s main subsidiary (running 8 refineries)
44
YOKOHAMAYOKOHAMA
MARIFUMARIFU
MURORANMURORAN
SENDAISENDAI
TOYAMATOYAMA
MIZUSHIMAMIZUSHIMAOSAKAOSAKA
MURORANSENDAIYOKOHAMANEGISHIOSAKAMIZUSHIMAMARIFUOITANPRC TotalTOYAMAKAINANGroup Total
180 kB/D145 kB/D
0 kB/D340 kB/D115 kB/D250 kB/D127 kB/D160 kB/D
1,317 kB/D60 kB/D
0 kB/D1,377 kB/D
KAINANKAINAN
NEGISHINEGISHI
(Nominal Capacities in June,2004)
OITAOITA
General Information on NOC/NPRCGeneral Information on NOC/NPRC
(28% of Japan Total ; 4,897 kB/D)
55
YOKOHAMAYOKOHAMA
MARIFUMARIFU
MURORANMURORAN
SENDAISENDAI
TOYAMATOYAMA
MIZUSHIMAMIZUSHIMAOSAKAOSAKA
MURORANSENDAIYOKOHAMANEGISHIOSAKAMIZUSHIMAMARIFUOITANPRC TotalTOYAMAKAINANGroup Total
180 kB/D145 kB/D
0 kB/D340 kB/D115 kB/D250 kB/D127 kB/D160 kB/D
1,317 kB/D60 kB/D
0 kB/D1,377 kB/D
KAINANKAINAN
NEGISHINEGISHI
(Nominal Capacities in June,2004)
(28% of Japan Total ; 4,897 kB/D)
OITAOITA
General Information of NOC/NPRCGeneral Information of NOC/NPRC
66
1. General Information on NOC/NPRC
2. Sulfur Regulations in Japan
3. Technology for Sulfur-free Diesel Fuel
4. Technology for Sulfur-free Gasoline
5. Production Process at Marifu Refinery
6. Conclusions
Agenda
77
Sulfur Standards in Japan “The road to Sulfur-free”
1.2% 0.5%0.2%
0.05%0.005%
(50 ppm)
1996 2005
0.01%(100 ppm)
0.005%(50 ppm)N/AGasoline
DieselFuel
2008
0.001%(10 ppm)
"Sulfur free"
～～
0.001%(10 ppm)
"Sulfur free"
～～
1953 1976 1992 1997 2005 2007
Deep Desulfurization
ULSD(Ultra-low sulfur diesel)
77
88
Sulfur Standards in Japan “The road to Sulfur-free”
1.2% 0.5%0.2%
0.05%0.005%
(50 ppm)
1996 2005
0.01%(100 ppm)
0.005%(50 ppm)N/AGasoline
DieselFuel
2008
0.001%(10 ppm)
"Sulfur free"
～～
0.001%(10 ppm)
"Sulfur free"
～～
Voluntary introductionVoluntary introductionof of ““SulfurSulfur-- freefree””
in 2005in 2005
1953 1976 1992 1997 2005 2007 88
99
Reasons for Reducing Sulfur in Diesel FuelReasons for Reducing Sulfur in Diesel Fuel
PollutantPollutant MeasuresMeasures ObstructionObstruction
SOxSOx Decreasing SulfurDecreasing Sulfur
NOxNOx EGR SystemEGR System SulfurSulfur(Exhaust Gas Recirculation)(Exhaust Gas Recirculation)
PMPM DPF SystemDPF System SulfurSulfurParticulateParticulate (Diesel Particulate Filter)(Diesel Particulate Filter)
MattersMatters
Decreasing sulfur will indirectly reduce NOx and PM.
Measures for Diesel Exhaust Gas EmissionMeasures for Diesel Exhaust Gas Emission
1010
Diesel Sulfur Regulations
mass ppm
2002 2003 2004 2005 2006 2007 2008 2009 2010
EPA
CARB
● 50 Max ● 10 MaxEU
350 Max
500 Max
500 Max
500 MaxUS
● 15 Max (06.6-)
● 15 Max
Japan
Year
● 50 Max
○ 10 Max
● 10 Max
○ 50 Max ○ 10 Max
voluntary
Japanese oil companies voluntarily reducedsulfur levels to less than 10 ppm in 2005.
1111
mass ppm
Japan is the world’s sulfur-free frontrunner.voluntary
2002 2003 2004 2005 2006 2007 2008 2009 2010
100 Max
1000 Max
150 Max
● 60 (Cap) ● 30 (Cap)
EU● 50 Max ● 10 Max
● 300 Max
30 (Avg.)
○ 10 Max
Year
● 50 Max ● 10 MaxJapan
○ 10 Max
US
CARB
● 20 (Flat)
80 (Cap)
40 (Flat)
EPA● 30 (Avg.)
● 15 (Avg.)
● 80 Max
Gasoline Sulfur Regulations
1212
1. General Information on NOC/NPRC
2. Sulfur Regulations in Japan
3. Technology for Sulfur-free Diesel Fuel
4. Technology for Sulfur-free Gasoline
5. Production Process at Marifu Refinery
6. Conclusions
Agenda
1313
0.1
1
10
100
1,000
10,000
100,000
WRN KERO DGO VGO AR
Sulfur,
mas
s pp
m
90%95%
97% (500 ppm)99%
99.7%
Feed
Produc
t
99.7% (50 ppm)
99.93% (10 ppm)
Sulfur Removal from Petroleum
1313
1414Boiling point, deg.-C
340 360 380 400 420
GC
-A
ED
, In
tensi
ty
Feed LGO Sulfur
14300 ppm
HDS LGO
×400
Remainingsulfur
50 ppm
Refractory Sulfur Compounds
4,6-dimethyl-dibenzothiopheneand its derivatives
R
SCH3 CH3
1414
1515
S SS
Easy Difficult
Relativereactivity*
9100 6
*Houalla et al., AIChE J. 24, 1015 (1978)
Boiling point 339 366
DBT 4,6-DMDBT
HDSHDS
Reactivity of Sulfur Compounds
1515
1616
k = A exp(-Ea / RT) = LHSV/(n-1) * (Spn-1 – Sfn-1)
k: rate constant
A: frequency factor
Ea: activation energy
R: gas constant
T: reaction temperature
n: reaction order
Sp: product sulfur
Sf: feedstock sulfur
A(cat.)*α(ppH2)*β(H2/Feed)*γ(H2S)*δ(Feed)
Reaction Kinetics
1717
500 ppm 50 ppm 10 ppm
Base x 4 x 8
Required Amount of Catalyst
1818
Key Factors for SulfurKey Factors for Sulfur--free Diesel Fuel free Diesel Fuel
Untreated Diesel Fuel
Product
HD
S Reactor
(1) Light Cut Distillation
(3) Increasing ofReactor Volume
(2) Enhancement of Catalyst Activity
(4) Increasing of HydrogenPartial Pressure
1919
Achieving SulfurAchieving Sulfur--free Diesel Fuel free Diesel Fuel
To meet the sulfur spec. of 50 ppm...(1) Optimization of Process Conditions
Effect of Feedstock PropertiesEffect of H2 Pressure, H2/Feed Ratio
(2) Development of New HDS Catalysts
To meet the sulfur spec. of 10 ppm...(1) Development of New HDS Catalysts
(abbrev.)
2020
Feedstock T90 and Refractory Sulfur
0100200300400500600
320 330 340 350 360 370
Ref
ract
ory
sulfu
r, m
ass
ppm
Feedstock T90, deg-C
R
SCH3 CH3
2121
Feedstock T90 and 3R+ Aromatics
0
2
4
6
8
10
280 300 320 340 360 380
3R+
arom
atic
s, v
ol%
Feedstock T90, deg-C
R
+ More rings
2222
Effect of Feedstock T90 on HDS Activity
0.5
1.0
1.5
2.0
2.5
3.0
320 330 340 350 360 370Feedstock T90, deg-C
(100% Arabian Light Crude)R
elat
ive
HD
S a
ctiv
ity
2323
S
Direct Route
4,6-DMDBT (sterically hindered, less reactive)
HydrogenationRoute
S
The Routes of Hydrodesulfurization
This route makes it easier to eliminate sulfur.
2424
NHS92
NHS99
NHS101
NHS204
NHS231
for50 ppm
for500 ppm
for 10 ppmR
ela
tive
activi
ty
Activity of NOC-Developed Catalysts
2424
2525
Negishi
Muroran
Sendai
Marifu
315m3
NHS-231NHS-204NHS-264
ToyamaMizushima
1,300 m3
Commercial Results (10 ppm sulfur)
2525
2626
10 ppm10 ppm10 ppm
x 4x 8
NewCatalyst
x 2.5
OtherFactors
Adding a New Reactor orReplacing an Existing Reactor
(Base: 500 ppm)
Overview of Sulfur-free Process
2727
1. General Information on NOC/NPRC
2. Sulfur Regulations in Japan
3. Technology for Sulfur-free Diesel Fuel
4. Technology for Sulfur-free Gasoline
5. Production Process at Marifu Refinery
6. Conclusions
Agenda
2828
CCG (FCC Gasoline)Catalyst Cracked Gasoline
ReformerReformer
FCCFCC
TopperTopper
RegularRegularGasolineGasoline
ReformateReformateNaphthaNaphtha
CrudeCrudeOilOil
BottomBottomFractionFraction
Regular Gasoline Production at Refinery
2929
0 50 100Blend ratio, %
CCG
Reformate
Others
0 100 200Sulfur, mass ppm
For Regular Gasoline
Gasoline Components and Sulfur in Japan
3030
+ ４H2S
Thiophene
+ H2S
+ H2R1R2
Olefin
R2R1
Thiophene HDS and olefin hydrogenation occur simultaneously.
Reaction Model of CCG-HDS
Paraffin
Paraffin
3131
R2R1
H
H
H
H
H2R2R1
H
H
RON 90RON 90RON 90 RON ＜80RON RON ＜＜8080
ParaffinParaffin
Paraffin40%
Paraffin40%
Olefin40%
Olefin40%
Aromatics20%
Aromatics20%
Olefin Hydrogenation in CCG-HDS
3232
Sulfur, m
ass
ppm 300
200
100
0
80
60
40
0
20
100806040 180120 140 160 200
Ole
fin, vo
l%
Boiling point, ℃
Light Fraction
Heavy Fraction
Distribution of Sulfur and Olefin
3333
Selective Desulfurization of CCGSelective Desulfurization of CCG
60
70
80
90
0 20 40 60 80 100Olefin hydrogenation，%R
esea
rch
octa
ne n
umbe
r
Selective HDS ProcessSCAN Fining (EM)Prime G+ (Axens)ROK-Finer (NOC)
Suppress
Promote
Improvement of both is necessary
3434
Process Performance of ROKProcess Performance of ROK--FinerFiner
10ppm
75
80
85
90
0 100HDS, ％
RO
N
Naphtha HDS
5070
RON of the Feedstock
ROK -Finer(RON Keeping)
(Feedstock Sulfur 80ppm)
3535
Simplified Diagram of ROKSimplified Diagram of ROK--FinerFiner
L/H Splitter
H-CCG HDSSection
Whole-CCG
L-CCG (S<10ppm)
H2
H-CCG(S<10ppm)
HDS% < 90%ΔRON < 2
• Process like Naphtha-HDS• Special Catalyst Developed by NOC
Selective HDS
3636
Flow Diagram of ROKFlow Diagram of ROK--FinerFiner
Hy CCG Product
Bleed Gas Off Gas
Stabilizer
Make up H2
Rx
Fu
Aminesection
O2 stripperSweetening
section
3737
SendaiMizushima
Negishi
Octane loss minimized Octane loss minimized by optimizingby optimizing・・reaction conditions reaction conditions ・・catalystcatalyst
ROK-Finer : Start-up in 2004
3838
VGO-HDSRDS
FCC CCG-HDSSulfur 10ppmCCG
VGO-HDS FCCSulfur 10ppmCCG
1. After-treatment (Introduction of CCG-HDS)
2. Pre-treatment (Load-up of VGO-HDS)
S = 50-100ppmS > 2000ppm
S < 500ppm
Methods of S=10ppm CCG ProductionMethods of S=10ppm CCG Production
3939
○○1601607. OITA7. OITANoneNoneNoneNone1271276. MARIFU6. MARIFU
○NoneNone2502505. MIZUSHIMA5. MIZUSHIMANoneNoneNoneNone1151154. OSAKA4. OSAKA
○○3403403. NEGISHI3. NEGISHI○○1451452. SENDAI2. SENDAI
NoneNoneNoneNone1801801. MURORAN1. MURORAN
CCGCCG--HDSHDSRFCCRFCCCDUCDU[kB/D][kB/D]RefineryRefinery
Methods of S=10ppm CCG ProductionMethods of S=10ppm CCG Production
Comparison of NOC/NPRC Refineries
4040
1. General Information on NOC/NPRC
2. Sulfur Regulations in Japan
3. Technology for Sulfur-free Diesel Fuel
4. Technology for Sulfur-free Gasoline
5. Production Process at Marifu Refinery
6. Conclusions
Agenda
4141
MARIFUMARIFU
MURORANMURORAN
SENDAISENDAI
MIZUSHIMAMIZUSHIMAOSAKAOSAKA
NEGISHINEGISHI
(Nominal Capacities in June,2004)
OITAOITA
MARIFU RefineryMARIFU Refinery
YAMAGUCHI Prefecture Operating since 1943 Crude Run Capacity: 127 kB/D
4242
Refining Block Flow / Marifu
Calcining
CrudeOil
LPG
Gasoline
Xylene
Fuel Oil
DGO
Kerosene
Coker
VGO HDS
GO-HDS
Kero-HDS
BenzeneToluene
Naphtha
Raw Coke
Calc’d Coke
FCC
CCRPlatforming
V D U
C
D
U
Aroma. Prod. U
Asphalt
127kBD
4343
Refining Block Flow / Marifu
Calcining
CrudeOil
LPG
Gasoline
Xylene
Fuel Oil
DGO
Kerosene
Coker
VGO HDS
GO-HDS
Kero-HDS
BenzeneToluene
Naphtha
Raw Coke
Calc’d Coke
FCC
CCRPlatforming
V D U
C
D
U
Aroma. Prod. U
Asphalt
127kBD
4444
VGO-HDS
Naph
Kero
DGO S<10ppm
VGO S<300ppm
GO-HDS
DGO S<10ppm
FCC CCG S<15ppm
Sulfur-free Diesel Fuel
Sulfur-free Gasoline
Other Blendstocks
Production Process at Marifu Refinery
MHC: Conv.= 20 to 40%
Feed-stock
Feed-stock
4545
VGO-HDS
Naph
Kero
DGO S<10ppm
VGO S<300ppm
GO-HDS
DGO S<10ppm
FCC
Sulfur-free Diesel Fuel
Production Process at Marifu Refinery
Feed-stock
Feed-stock
Online Sulfur Analyzer (for 10ppm)Checking value against laboratory analysis periodically.
CCG S<15ppm
Sulfur-free Gasoline
Other Blendstocks
4646
Sulfur Content of Product OilDesulfurized Gas Oil (GO-HDS)
05
1015202530
0 100 200 300 400 500 600 700DaysP
rodu
ct S
ulfu
r (m
ass
ppm
)
CCG (FCC)
05
1015202530
0 100 200 300 400 500 600 700DaysP
rodu
ct S
ulfu
r (m
ass
ppm
)
4747
1. Japanese oil companies have been voluntarily producing “Sulfur-free; 10ppm” products since 2005. (The world’s front-runner)
2. Nippon Oil has developed technologies for sulfur-free fuels production.
Diesel fuel: High activity HDS catalysts
Gasoline: ROK-Finer process(Selective CCG-HDS)
3. Our commercial units are now operating smoothly to produce sulfur-free fuels stably.
Conclusions
4848
Thank you very much for your kind attention.
4949
Additional sheetsAdditional sheets
50502θ
Inte
nsi
ty
20 40 60 80
NHS-101
MoO3
NHS-99
Well dispersed
NHS-92
5050
XRD Patterns for GO-HDS Catalysts
5151
0
10
20
30
40
50
0 100 200 300 400 500 600
Days
Pro
duct
sulfur, m
ass
ppm
10ppm operation
5151
NHS-204 in Commercial Operation
5252
0
10
20
30
40
0 100 200 300 400 500 600
days
Pro
duct
sulfur, m
ass
ppm
The simulator we developed helps achieve product sulfur levels less than 10 ppm.
5252
Product Sulfur at Sendai (ROK-Finer)
5353
Design
Actual
80 85 90 95HDS, %
⊿R
ON
base
-2
+2
+4
+6
5353
HDS Selectivity at Sendai (ROK-Finer)
5454
0
5
10
15
20
Thiol
Total sulfurThiophene
S
R2R1SH
existed in feed
Base +1 +2 +3 +4Hydrogen Partial Pressure, MPa
Pro
duct
sulfur, m
ass
ppm
5454
Sulfur Types in CCG-HDS Product
5555
+ ４H2S
thiophene
+ H2S
+ H2R1R2
olefin
R2R1
+ H2SR1R2
olefin
R2R1SH
thiol
It is important to understand the mechanism ofIt is important to understand the mechanism ofthiol formation.thiol formation.
Reaction Model of CCG-HDS
5656
Introduction of NOC Introduction of NOC -- Refinery Configuration Refinery Configuration --
22%252252282846462727818140403030FCC/RFCCFCC/RFCC
35%40540544448282464614214229296262MDMD--HDSHDS
10%118118353511117272HDC/MHCHDC/MHC
2%22222222CokerCoker
2%
13%
15%
17%
100%
22225544101033Asphalt IPPAsphalt IPP
17817813133737212172723535VGOVGO--HDSHDS
1491494545363652521616ARDS/VRDSARDS/VRDS
14.814.816.116.114.114.113.613.617.417.412.912.912.312.3C.F.C.F.
193193242448481717505018183636ReformerReformer
1,1571,157127127250250115115340340145145180180CDUCDU
TotalTotalMarifuMarifuMizushimaMizushimaOsakaOsakaNegishiNegishiSendaiSendaiMuroranMurorankB/DkB/D
