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
AGENDA
2
• RFCC UNIT AT RUWAIS
• RFCC CATALYST
• COMMON CATALYST DEACTIVATION
PROTOCOLS
• BASIS OF THE NEW APPROACH.
• SUMMARY
◼ 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
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
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
RFCC CATALYST
6 Hierarchical pore structure in a RFCC
catalystHagen, J. (2015). Industrial catalysis : A practical approach
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
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)
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
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.
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
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
TEMPERATURE EFFECT
13
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%
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.
ABU DHABI NATIONAL OIL COMPANYADNOC REFINING
THANK YOU
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