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DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ......

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ABU DHABI NATIONAL OIL COMPANY ADNOC REFINING DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN COMMERCIAL RFCC CATALYSTS SPEAKER: ABDULMAJEED ALKATHEERI [email protected]
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Page 1: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

ABU DHABI NATIONAL OIL COMPANYADNOC REFINING

DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN COMMERCIAL RFCC CATALYSTS

SPEAKER: ABDULMAJEED ALKATHEERI

[email protected]

Page 2: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

AGENDA

2

• RFCC UNIT AT RUWAIS

• RFCC CATALYST

• COMMON CATALYST DEACTIVATION

PROTOCOLS

• BASIS OF THE NEW APPROACH.

• SUMMARY

Page 3: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

◼ 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

Page 4: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 5: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 6: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

RFCC CATALYST

6 Hierarchical pore structure in a RFCC

catalystHagen, J. (2015). Industrial catalysis : A practical approach

Page 7: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 8: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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)

Page 9: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 10: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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.

Page 11: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 12: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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

Page 13: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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%

Page 14: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

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.

Page 15: DEVELOPMENT ON CATALYTIC DEACTIVATION STUDY IN … · • RFCC UNIT AT RUWAIS • RFCC CATALYST ... flue gas from cat RFCC OPERATION 5. RFCC CATALYST 6 Hierarchical pore structure

ABU DHABI NATIONAL OIL COMPANYADNOC REFINING

THANK YOU

15


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