ABU DHABI NATIONAL OIL COMPANYADNOC REFINING

DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN COMMERCIAL RFCC CATALYSTS

SPEAKER: ABDULMAJEED ALKATHEERI

AMALKATHEERI@ADNOC.AE

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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