A New Olefins Selective Cracking Catalyst for Maximum

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

Background


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)


High Propylene Yield from FCC

Factors

Feed

Severity

Catalyst

(K.A. Couch, et al., www.eptq.com, PTQ, Q3 2007)

CAN-FCC Catalyst


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.


CAN-FCC-Optimized acid properties

Ti,Zr-Insertion → Enhanced medium strength acid sites


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 -

Evaluation Testing


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.)


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


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


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)


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

Results and Discussion


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


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%.


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%


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%.


Yield Comparison

– Dry Gas, Coke


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%)


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%)


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


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.


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.


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


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.


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?

Documents

A New Olefins Selective Cracking Catalyst for Maximum