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A New Olefins Selective

Cracking Catalyst for


Maximum Propylene
Production from FCC Units
YAMING 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


Outline

 Background
 CAN-FCC Catalyst
 Evaluation Tests
 Results and Discussion
 Summary and Conclusion
 Acknowledgement

Saudi Aramco: Public


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)

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High Propylene Yield from FCC

 Factors

Feed

Severity

Catalyst

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

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CAN-FCC Catalyst
CAN-FCC
- An Olefin-Selective Catalyst Based on Ti-Zr Inserted USY Zeolite

Ti-Zr inserted USY zeolite, which enhances the medium strength acid sites, leads to
high olefin selectivity in hydrocarbon cracking.

❖ Micropores ❖ Micropores ❖ Micropores


❖ Si/Al2: ~5 ❖ Mesopores ❖ Mesopores
❖ Si/Al2 > 5 ❖ Si/Al2 > 5
Saudi Aramco: Public ❖ M- framework insertion
CAN-FCC
-Optimized acid properties

 Ti,Zr-Insertion → Enhanced medium strength acid sites

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CAN-FCC
- Physical properties similar to those of standard FCC
catalysts

Standard
Analysis CAN-FCC FCC* Spec
LOI (%) 10.10 11.47 <15.0

BET SA (m 2/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 -
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Evaluation Testing
Testing Conditions

Gasoline* HP FCC* HS FCC*


mode mode mode

Feed FCC VGO FCC HCB HCB-1


Cracking T (°C) 515 530 600
C/O 3-6 4-8 10 - 11

CAN-FCC CAN-FCC CAN-FCC


Catalyst** Vs. Vs. Vs.
Fcat 1 Fcat 2 Fcat 3

* HP FCC = High propylene mode FCC; HS FCC = high sev erity mode FCC.
5-10% JGC C&C’s OCTUP- ZSM-5 additiv e was included in the catalyst loads.
** Catalyst/additiv e deactiv ation using ASTM D4463 method (100% steam at 810°C for 6
hours.)
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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

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Catalyst Circulating Riser Pilot Plant
Schematic Diagram of FCC Pilot Plant

REGENERATOR

WTM-2 STABILIZER
BPR-601 STRIPPER V-505

V-504
GC
V-503
PCV-601 H.E.-501
H.E.-601 LIFT C-501
LINE F-501

V-501
D-502

LI-2 D-601

S.V.-101 SG-502
RISER
WTM-1
BPR-501
LCV-2 S.V.-401 V-111
V-602 GC
V-603
LI-1 V-110 V-112

FEED VESSEL
PCV-501
LCV-1

PRODUCT VESSEL
PR P-51

V-604

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Feed Properties

Feed
FCC VGO FCC HCB HCB-1*
Property

Density (D-4052),
0.8986 0.8164 0.8427
gm/cc

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)
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Feed SimDist

1200

1100 HCB-1
FCC-HCB
1000
FCC-VGO
Temperature (°F)

900

800

700

600

500

400

300
0% 20% 40% 60% 80% 100%

% Distilled volume
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Results and Discussion
Cracking Activity

 CAN-FCC has a slightly lower cracking activity, at the same severity:

100
CAN-FCC
~ 1%
Fcat
95
Conversion (%)

~ 2%
90

85

80
HP FCC HS FCC

HCB feed, pilot plant data


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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%.

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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%
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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%.
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Yield Comparison
– Dry Gas, Coke

Gasoline Mode Product CAN-FCC Fcat-1  (CAN - Fcat)


(ACE conv. 70%)
Dry Gas (%) 1.55 1.55 0

Ethylene (%) 0.76 0.71 0.05

Coke 2.38 3.10 -0.72

HP FCC Product CAN-FCC Fcat-3  (CAN - Fcat)


(PP conv. 94%)
Dry Gas (%) 2.43 1.78 0.66
Ethylene (%) 2.01 1.32 0.68
Coke 1.25 1.75 -0.50

HS FCC Product CAN-FCC Fcat-3 SATORP-Fcat


(PP conv. 96%) Dry Gas (%) 5.74 4.25 1.49
Ethylene (%) 3.95 2.49 1.46

Coke 1.17
Saudi Aramco: Public 1.39 -0.22
Yield Comparison
– FCC Naphtha

Olefins Paraffins Naphthene Aromatics


(%) (%) (%) (%)

HP FCC
8.5 -7.5 1.9 -2.9
(530°C, PP Conv. 94%)

HS FCC
4.8 -6.1 2.4 -1.1
(600°C, PP Conv. 96%)

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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.

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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.

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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

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Takeaways
(The Conference Chairman, M r. 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.

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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?

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