2007 日本―中国―韓国 石油技術会議

Heavy Oil Upgrading Technologies Coupled

with Solvent Deasphalting Process

December 5, 2007

永松茂樹
（ Shigeki Nagamatsu）

JGC Corporation
6D01IJ001
 Contents

Background of Heavy Oil Upgrading Technologies

Solvent Deasphalting Process Coupled with
Hydrotreating Process as Pretreater for FCC
Utilization of SDA Pitch
Residue Water Mixture (RWMTM)
Pitch as Cokes Binder for Steel Making

2
 Contents

Background of Heavy Oil Upgrading Technologies

Solvent Deasphalting Process Coupled with

Hydrotreating Process as Pretreater for FCC
Utilization of SDA Pitch
Residue Water Mixture (RWMTM)
Pitch as Cokes Binder for Steel Making

3
 Heavy Oil Upgrading Processes

Fixed Bed
Hydrogen HDS
HCR Ebullated Bed
Addition
Slurry

Thermal Visbreaker
Cracking
Upgrading Coker
Technologies
Carbon Catalytic
FCC, RFCC
Rejection Cracking

Solvent
Extraction SDA

Other
Gasification
Technologies
44
 Residue Properties and Process Selection
Properties of 650℃+ (343℃+) Boiling Point Residues
20
Venezuelan
Canadian Zuata
Cold Late Mexican
Maya
Carbon Residue( wt%)

15 Arabian
Heavy
Venezuelan
Alaskan Bachaquero
North Slope
10

Catalytic Cracking
Range Arabian
5 Light

Hydroprocessing Thermal Processing

Range Region

0
1 10 100 1000 10000
Ni + V (wtppm) Source: SFA Pacific 5
 Heavy Oil Upgrading Process (1)

Thermal Cracking
AR

HDS FCC Gasoline

VGO

Hydrocracking

Vacuum Distillates
Distillation

Hydrotreating
VR
Delayed
Coker

Coke
Fuel
Drawbacks
Lower liquid yield
Low stability of products 6
 Heavy Oil Upgrading Process (2)
AR SDA (Solvent De-asphalting)
HDS FCC Gasoline
VGO

Vacuum Hydrocracking
Distillation
Distillates

DAO
VR
SDA

SDA Pitch
Fuel
Drawbacks
DAO to be subject to cracking process
Pitch utilization 7
 Heavy Oil Upgrading Processing (3)

SDA + RWM
AR

HDS FCC Gasoline

VGO

Vacuum Hydrocracking
Distillation
Distillates

DAO
VR
SDA Fuel
Liquid Fuel
RWM
SDA Pitch
Cokes Binder
Treatment for
Steel Making
8
 Contents

Background of Heavy Oil Upgrading Technologies

Solvent Deasphalting Process Coupled with

Hydrotreating Process as Pretreater for FCC
Utilization of SDA Pitch
Residue Water Mixture (RWMTM)
Pitch as Cokes Binder for Steel Making

9
 Effect of SDA and HDMS on FCC Operation

SDA ：Solvent deasphalting

HDMS ：Hydrodemetallization and desulfurization

Increasing Increase in ・Increase in profit

hydrogen gasoline
content yield
・Decrease in catalyst
Decrease in regeneration severity
Decreasing coke yield
CCR ・Increase in throughput

Decrease in
Decreasing ・Decrease in catalyst
catalyst
metals consumption
degradation
1
0
 Various Pilot Tests of SDA and HDMS

DAO DS-DAO
AR,VR SDA HDMS FCC Products

100 1.0 3.0

Extraction Ratio to DAO [%]

Sulfur, Nitrogen [wt%]

80
2.0

C C R [wt %]
CCR
60
Sulfur 0.5
Nitrogen
40 CCR
Sulfur 1.0
20 Vanadium
Nickel Nitrogen
0 0.0 0.0
40 50 60 70 80 90
DAO Yield on SDA [wt% ] Reaction Temperature

Solvent: C3~C5
CCIC’s CDS Series Catalyst
S/O : 2~8 v/v
CDS-DM5CQ
Temp. : Sub-supercritical
CDS-R25NQ
Press. : Supercritical 11
 Properties of Feed AR and DAO

HDMS DS-AR
385 ℃, 135kg/cm2
AR AR-DAO
SDA HDMS DS-ARDAO
Yield 85wt% 350 ℃, 81kg/cm2

Sample ID AR DS-AR AR-DAO DS-AR

DAO
Dens. g/cm3 0.971 0.914 0.941 0.911
Sulfur wt% 3.95 0.18 3.30 0.33
Total-N wtppm 2100 705 1580 800
CCR % 11.1 3.2 4.3 1.3
Ni+V wtppm 65 3.4 16 <0.5
 Evaluation of SDA and HDMS
on FCC Performance

DAO DS-DAO
AR,VR SDA HDMS FCC Products

Operating conditions of ACE-MAT

Catalyst： Equilibrium RFCC catalyst
（V : 4500wtppm, Ni :2530wtppm）
Ope. Temperature： 530℃
Catalyst/Oil ratio ： 3.75～6.0

13
 Effect of SDA on FCC Performance
in terms of DAO Yield
HDMS： 360℃, 100 bar
60 900
Gasoline Yield on DAO

Estimated Sulfur content

in FCC gasoline [ppm]
Estimated Yield [wt%]

40 600

Gasoline Yield on VR

20 300
Coke Yield on VR

0 0
40 50 60 70
DAO Yield [wt% ]
14
 Effect of HDMS on FCC Performance
in terms of Reaction Pressure

2 400
FCC Yield Change [wt%] Gasoline Yield

Estimated Sulfur Content

in FCC Gasoline [wtppm]
1 300
Sulfur in Gasoline

0 200

Coke Yield
-1 100

-2 0
50 70 90 110 130 150
2
Reaction Pressure of HDMS [kg/cm ]
15
 Effect of SDA and HDMS on FCC Performance

DAO DS-DAO
AR SDA HDMS FCC Products
Yield 350℃
85wt% 90kg/cm2
Conversion 72.7
Sp.Gr. [-] 0.971 0.941 0.911
Gasoline 48.4
S [wt%] 3.95 16% 3.30 92% 0.33
Coke 5.7
CCR[wt%] 11.1 62% 4.3 88% 1.3
V+Ni [wtppm] 65 75% 16 99% <0.5

385℃
135kg/cm2
0.914 Conversion 74.7
95% 0.18 Gasoline 49.0
a%
71% 3.2 Coke 7.1
b% Reduction on AR 99% <0.5
c%

16
 Summary

Effect of SDA and HDMS on FCC Operation

SDA is effective for removing CCR and metals

from residue.
SDA can reduce operating severity of
hydrotreating (HDMS) and can be a suitable
pretreater for HDMS.
By combining SDA and HDMS, higher yield of
gasoline and lower yield of coke can be
obtained in FCC operation from residue.

17
 Contents

Background of Heavy Oil Upgrading Technologies

Solvent Deasphalting Process Coupled with
Hydrotreating Process as Pretreater for FCC

Utilization of SDA Pitch

Residue Water Mixture (RWMTM)
Pitch as Cokes Binder for Steel Making

18
 TM
RWM ： Residue Water Mixture
RWM =Residue(70%) + Water(30%) + Additives(<1%)

Highly Loaded Residue Water Mixture

Liquid fuel similar to heavy fuel oil

Closed storage & transportation
No explosion hazard
No dust problem

19
 TM
What is RWM

Additives Particle Size Distribution

Coagulation
Pitch

hydrophobic
additives

Additive gives
electrical
repulsive force
to pitch

20
 RWMTM Mixing Process

Additives
Water
Fluidizing Dispersing
SDA Stabilizing
Pitch

Pitch Hopper Service Tank

Mixer

21
 Results of Experiments

RWMTM CWM Orimulsion

Raw Material TM SDA Pitch Coal Orinoco Tar
RWM has similar properties to
other
Contents, wt% 69 ±1
commercialized process.72±1
70

Viscosity , 1,000 1,000 <900

cP @30℃
Specific Gravity 1.1 1.2 1.01

Heating Value(HHV), 6,660 5,200 6,900 – 7,300

Kcal/kg
Particle size, μm 33.5 33.8 23-24
Mean dia. of volume
22
 Contents

Background of Heavy Oil Upgrading Technologies

Solvent Deasphalting Process Coupled with
Hydrotreating Process as Pretreater for FCC

Utilization of SDA Pitch

Residue Water Mixture (RWMTM)

Pitch as Cokes Binder for Steel Making

23
 SDA Pitch Used in Experiment

Sample V*1 A*2 B*2 C*2

SDA Feed AR AR VR AR
SDA Solvent Butane Butane Butane Propane
S.P [deg.C] 188 110 137 89
H/C [mom/mol] 1.20 1.22 1.17 1.32
HS [wt%] 31.3 38.5 48.1 81.2
HITS [wt%] 68.4 61.4 51.5 18.7
TI [wt%] 0.3 0.2 0.4 0.1
HS: Hexane Soluble, HITS: Hexane Insoluble & Toluene Soluble,
TI: Toluene Insoluble *1 South American Crude
*2 Middle east crude

SDA Pitch
(~3mm) Carbonization
Cokes strength
+ Cokes measurement
Coal with (DI150 15)
Noncaking coal
(~3mm)
24
 Effect of SDA Pitch Addition on Cokes Strength

86.0 Required value

as cokes for
85.5 steel making
[-]

85.0
15

84.5
150

84.0
DI

83.5
83.0
e h ) h ) h ) h )
c
r en ti c ti c ti c ti c
e - P - P - P P
ef R R R R-
R (A (A (V (A
V A B C

SDA Pitch
SDA Pitch: 3%,
Coal including 40% noncaking coal 25
 Effect of Heat Treatment of SDA Pitch
on Cokes Strength

86.0
VR Pitch (B) with heat treatment
85.5 Treated at 420℃ for 40 min
HS : 48.1→ 33
HITS : 51.5→ 35
[-]

85.0 TI : 0.4→ 32
15

84.5
150

AR Pitch (V)
84.0
DI

83.5
0.5
83.0
0 2 4 6 8
SDA Pitch Content [wt%]
26
 Function of SDA Pitch as Cokes Binder

Light fraction (HS) of pitch gasifies and accelerates growth

and coalescence of bubble in melted coal. Then bubble
grows with an appropriate size. However, excess amount of
HS decreases strength of cokes.
⇒Heat treatment of pitch is effective to control HS
content of pitch.
Middle fraction (HITS) lowers viscosity of melted coal and
forms appropriate bubble shape.
Heavy fraction (TI) increases thickness of cokes wall.
⇒Heat treatment of pitch is effective to increase TI
content
SDA Pitch is a suitable material as a binder which makes
noncaking coal good-quality cokes for steel making.
27
 Summary

SDA can reduce operating severity of

hydrotreating (HDMS) and can be a suitable
pretreater for FCC process
RWMTM can deal with SDA pitch by producing
liquid fuel and could be useful process to utilize
the pitch.
SDA Pitch is a suitable material as a binder
which makes noncaking coal good-quality
cokes for steel making

28
Thank you for your attention !

謝 謝

감사합니다

ご清聴ありがとうございます。
29