development on catalytic deactivation study in … · • rfcc unit at ruwais • rfcc catalyst ......
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ABU DHABI NATIONAL OIL COMPANYADNOC REFINING
DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN COMMERCIAL RFCC CATALYSTS
SPEAKER: ABDULMAJEED ALKATHEERI
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AGENDA
2
• RFCC UNIT AT RUWAIS
• RFCC CATALYST
• COMMON CATALYST DEACTIVATION
PROTOCOLS
• BASIS OF THE NEW APPROACH.
• SUMMARY
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◼ Ruwais refinery, Abu Dhabi
◼ Resid to propylene technology, R2R
technology
◼ 127,000 BPSD
◼ PetroRiser recycling LCN
◼ Atmospheric Residue,
API=21,
CCR=4.7 %, S = 1.7 wt%
Nickel:7 ppmw
Vanadium:11 ppmw
ADNOC REFINING RFCC UNIT
3
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RUWAIS REFINERY RFCCDOWNSTREAM UNITS
AD
NO
C R
EF
ININ
G | P
RE
SE
NT
AT
ION
TIT
LE
4
Slurry oil
Delayed Coker
Carbon Black
LCO Mild Hydrocracker
RF
CC
Cracked Naphtha
Propylene to export
Mixed C4s
C4 to alkylation
unit
Naphtha
hydrotreater
Olefins conversion
unit
Ethylene
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Operating Conditions(T,
C/O, Contact time)
Catalyst flow Control(velocit
y, flow regime)
Catalyst
Formulation
(Chemical & physical
properties)
To Achieve max
target of Product
Feed+Catalyst
Separate Products from cat
Regenerate catalyst
Separate flue gas from cat
RFCC OPERATION
5
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RFCC CATALYST
6 Hierarchical pore structure in a RFCC
catalystHagen, J. (2015). Industrial catalysis : A practical approach
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ACTIVITY OF RFCC CATALYST
7
Hypothetical activity
Operating activity
Equilibrium catalyst E-Cat
Act
ivit
y le
vel
F(C
oke
, Met
al, S
A)
Fresh activity
Non active catalyst
Time
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TEMPERATURE VS TIME
It is commonly practiced to increase the deactivation temperature to simulate the aging
effect.
8
B Darjaz. "Studies in Surface Science and Catalysis." Elsevier 24 (1985)
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DEACTIVATION STEPS
9
Tem
pe
ratu
re °
CCracking step Steaming
Time
780
Regeneration
Feed Spiked with
metals: NI,V
Air atmosphere Steam
End of deactivation
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DEACTIVATION EQUIPMENT
AD
NO
C R
EF
ININ
G | P
RE
SE
NT
AT
ION
TIT
LE
10
Hydrocarbon Feed
Water
Gases
T=780
°C
Bubbling
fluidized
bed
Findings:
At certain level of concentration
catalyst can not take up the
metals.
Clusters form at the inlet of the
reactor.
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DEACTIVATION
11
Base catalyst Metallation at 780 °C and steaming at 800°C for 6
hours
Olefins Additives
Steaming at 800 °C for 20
hours
Deactivated catalyst for
testing kinetics
Base catalyst Metallation at 650°C and steaming at 800°C for 6
hours
Olefins Additives
Steaming at 800 °C for 20
hours
Standard
Protocol
Modified
Protocol
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Catalyst
Bed
Fixed
fluidized
Bed
Reaction
Temp
550 °C
Cat/Oil 4-9
WHSV 8
Contact
time
< 3
seconds
Evaluation UnitAdvanced Cracking Evaluation Evaluation Conditions
EVALUATION OF CATALYST
12
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TEMPERATURE EFFECT
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60
65
70
75
80
85
90
2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5
CO
NV
ER
SIO
N W
T%
CAT/OIL WT/WT
CONVERSION VS CAT/OIL
Cat A @650 °C Cat A @780 °C
Δ > 5%
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SUMMARY
14
• Effect of cracking temperature is dominant in
deactivating the catalyst.
• Wet metallation at low temperatures will give
Lower deactivation effect. On the contrary
increasing temperature too high will agglomerate
metals.
• It is found that cracking at low temperatures
better simulate metal distribution of E-Cat.
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ABU DHABI NATIONAL OIL COMPANYADNOC REFINING
THANK YOU
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