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A New Olefins Selective
Cracking Catalyst for Maximum Propylene
Production from FCC UnitsYAMING JIN AND OMER R. KOSEOGLU (ARAMCO R&DC)MITSUNORI WATABE, SEIJI ARAKAWA AND KENJI NITA (JGC C&C)
OCTOBER 23-25, 2018, BAHRAIN
© Saudi Arabian Oil Company, 2018
Saudi Aramco: Public
Outline
Background
CAN-FCC Catalyst
Evaluation Tests
Results and Discussion
Summary and Conclusion
Acknowledgement
Saudi Aramco: Public
High Propylene → High Margin
The propylene-gasoline price differential has been generally
positive, and is expected to be more so on the global market.
(R. Roux, Saudi Aramco-Axens’ seminar, Dhahran, 2010)
Saudi Aramco: Public
High Propylene Yield from FCC
Factors
Feed
Severity
Catalyst
(K.A. Couch, et al., www.eptq.com, PTQ, Q3 2007)
Saudi Aramco: Public
CAN-FCC- An Olefin-Selective Catalyst Based on Ti-Zr Inserted USY Zeolite
❖Micropores
❖Si/Al2: ~5
❖Micropores
❖Mesopores
❖Si/Al2 > 5
❖Micropores
❖Mesopores
❖Si/Al2 > 5
❖M- framework insertion
Ti-Zr inserted USY zeolite, which enhances the medium strength acid sites, leads to high olefin selectivity in hydrocarbon cracking.
Saudi Aramco: Public
CAN-FCC-Optimized acid properties
Ti,Zr-Insertion → Enhanced medium strength acid sites
Saudi Aramco: Public
CAN-FCC- Physical properties similar to those of standard FCC
catalysts
Analysis CAN-FCC
Standard
FCC* Spec
LOI (%) 10.10 11.47 <15.0
BET SA (m2/g) 278 276 -
Attrition Index* 1.1 2.5 -
Particle size distribution
less than 20 m (%) 2 2 <3
less than 40 m (%) 14 13 <15
less than 80 m (%) 71 55 >50
less than 150 m (%) 99 94 >95
APS (m) 65 76 -
Saudi Aramco: Public
Testing Conditions
Gasoline*
mode
HP FCC*
mode
HS FCC*mode
Feed FCC VGO FCC HCB HCB-1
Cracking T (°C) 515 530 600
C/O 3 - 6 4 - 8 10 - 11
Catalyst**
CAN-FCC
Vs.
Fcat 1
CAN-FCC
Vs.
Fcat 2
CAN-FCC
Vs.
Fcat 3
* HP FCC = High propylene mode FCC; HS FCC = high severity mode FCC.
5-10% JGC C&C’s OCTUP- ZSM-5 additive was included in the catalyst loads.
** Catalyst/additive deactivation using ASTM D4463 method (100% steam at 810°C for 6
hours.)
Saudi Aramco: Public
ACE Reactor
• Injection rate: 1.5 g/min
• Injection time: 45 Sec
• Feed line sweep: 20 sccm
• Top fluidization: 20 sccm
• Bottom fluidization: 100
sccm
Saudi Aramco: Public
Catalyst Circulating Riser Pilot Plant
Schematic Diagram of FCC Pilot PlantSchematic Diagram of FCC Pilot Plant
GC
PR
STABILIZER
LIFT
LINE
REGENERATOR
RISER
STRIPPER
S.V.-401
S.V.-101
V-505
V-503
V-504
F-501
H.E.-501
D-502
SG-502
V-111
V-110 V-112
PCV-501
C-501H.E.-601
BPR-601
GC
V-501
FEED VESSEL
P-51
V-602
V-603
LCV-2
LCV-1
V-604
PRODUCT VESSEL
WTM-1
WTM-2
PCV-601
LI-2
LI-1
BPR-501
D-601
Saudi Aramco: Public
Feed Properties
Feed
PropertyFCC VGO FCC HCB HCB-1*
Density (D-4052),gm/cc
0.8986 0.8164 0.8427
Sulfur (D4294), ppm 2.50 (wt.%) 70 32
Nitrogen, ppm 350 <5 <5
T90, (°F, D2887) 922 965 950
H-content, Wt.% 12.31 15.25 14.48
Total HPNA, ppm n.d. 50.2 214.3
(*2nd stage DHC Feed)
Saudi Aramco: Public
Feed SimDist
300
400
500
600
700
800
900
1000
1100
1200
0% 20% 40% 60% 80% 100%
Tem
pe
ratu
re (
°F)
% Distilled volume
HCB-1
FCC-HCB
FCC-VGO
Saudi Aramco: Public
Cracking Activity
CAN-FCC has a slightly lower cracking activity, at the same severity:
80
85
90
95
100
HP FCC HS FCC
Co
nve
rsio
n (
%)
CAN-FCC
Fcat
~ 2%
~ 1%
HCB feed, pilot plant data
Saudi Aramco: Public
Gasoline Mode Yield Comparison
– ACE Testing
Product CAN-FCC Fcat-1 (CAN - Fcat)
Gasoline (%) 39.3 41.9 2.6
LPG (%) 26.8 23.4 3.4
Propylene (%) 8.0 6.4 1.6
Butenes (%) 9.8 7.6 2.2
FCC-VGO feed, cracking temperature at 515°C, conversion at 70%.
Saudi Aramco: Public
HP FCC Mode Yield Comparison
– Pilot Plant Testing
Product CAN-FCC Fcat-3 (CAN – FCAT)
Gasoline (%) 47.6 52.7 -5.1
LPG (%) 42.6 37.6 5.0
Propylene (%) 15.6 13.0 2.6
Butenes (%) 17.2 14.2 3.0
LPG paraffins (%) 9.8 10.5 -0.7
HCB feed, cracking temperature at 530°C, 10% ZSM-5 additive,
conversion at 94%
Saudi Aramco: Public
HS FCC Mode Yield Comparison
– Pilot Plant Testing
Product CAN-FCC Fcat-3 (CAN – FCAT)
Gasoline (%) 39.4 45.3 -5.9
LPG (%) 49.4 44.8 4.6
Propylene (%) 21.5 17.4 4.1
Butenes (%) 20.0 18.5 1.5
LPG paraffins (%) 7.8 8.8 -1.0
HCB feed, riser temperature at 600°C, 10 wt.% ZSM-5 additive, C/O ratio of 10-11, and conversion at 95.7%.
Saudi Aramco: Public
Yield Comparison
– Dry Gas, Coke
Product CAN-FCC Fcat-3 (CAN - Fcat)
Dry Gas (%) 2.43 1.78 0.66
Ethylene (%) 2.01 1.32 0.68
Coke 1.25 1.75 -0.50
HP FCC(PP conv. 94%)
Product CAN-FCC Fcat-3 SATORP-Fcat
Dry Gas (%) 5.74 4.25 1.49
Ethylene (%) 3.95 2.49 1.46
Coke 1.17 1.39 -0.22
HS FCC(PP conv. 96%)
Product CAN-FCC Fcat-1 (CAN - Fcat)
Dry Gas (%) 1.55 1.55 0
Ethylene (%) 0.76 0.71 0.05
Coke 2.38 3.10 -0.72
Gasoline Mode (ACE conv. 70%)
Saudi Aramco: Public
Yield Comparison
– FCC Naphtha
Olefins(%)
Paraffins(%)
Naphthene(%)
Aromatics(%)
HP FCC
(530°C, PP Conv. 94%)8.5 -7.5 1.9 -2.9
HS FCC
(600°C, PP Conv. 96%)4.8 -6.1 2.4 -1.1
Saudi Aramco: Public
Summary
CAN-FCC catalyst, based on an innovative Ti-Zr inserted USY zeolite, was tested for three FCC application scenarios for improved propylene yields.
CAN-FCC meets all physical property specifications of standard FCC catalyst.
CAN-FCC has a slightly lower cracking activity than standard FCC catalyst.
For a HP FCC scenario at cracking temperature of 530°C using a HCB feed, CAN-FCC leads to 2.6% more propylene over the Fcat.
For a HS FCC scenario at 600°C using a HCB feed, CAN-FCC results in 4% more propylene over the Fcat.
For a typical gasoline FCC mode at 515°C using a VGO-FCC feed, CAN-FCC leads to 1.6% and 2.2% more propylene and butenes respectively than Fcat.
CAN-FCC has a slightly low coking selectivity, and somewhat higher dry gases mainly of ethylene.
Saudi Aramco: Public
Conclusion
CAN-FCC is a highly propylene selective catalyst.
CAN-FCC can be used to maximize LPG olefins
yield, especially propylene, under a rather wide feed and process conditions.
Saudi Aramco: Public
Acknowledgement
Dr. Ali Al-Somali for managerial support
Hamzh J Alhmadh, Amjed D Alshammari, Abdullah Bannai
Process engineering groups at RTR, JR, SATORP for F-Cat, Feeds
David S. Renolayan of DR&NGLF
Rengamannar Parthasarathi and Said A. Zahrani of Aramco
P&CSD
Tiju Joseph of TS&PD
KFUPM, ACE testing
CPERI, Pilot plant testing
Saudi Aramco: Public
Takeaways (The Conference Chairman, Mr. Suleman A. Al-Bargan – VP Domestic
Refining & NGL Fractionation of Saudi Aramco may include some of these takeaways in his closing ceremony speech.)
A highly olefin selective FCC catalyst, CAN-FCC based on an
innovative metal-inserted USY zeolite, was jointly developed by
Aramco R&D Center and Japanese JGC C&C Company.
The new development CAN-FCC catalyst significantly
increases the propylene and butenes yields under typical FCC
unit operation conditions.
As a mature industry, off-the-shelf vendor catalysts can do
most of the jobs in the refineries. However, in-house R&D
development effort can lead to new catalysts, which are
tailored for unit specifics such as feed properties, operation
constrains, and optimized product yield structure, and
therefore, maximize the operation margin.
Saudi Aramco: Public
3 Ice-breaker Questions
Do you have experimental proofs that show metal
modifiers, i.e., Zr, Ti, are inserted into the zeolite
framework?
What is the expected impact of zeolite modification
by insertion of metal atoms in zeolite framework on
the cost of the catalysts?
CAN-FCC catalyst seems to result in lower coke
yield than F-Cat. How do you plan to compensate
the required heat in the FCC system?