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Catalyst System Design for Robust

FCC-PT Performance

S. Eijsbouts, S. Melis, S. Mayo, L. Burns and G. Anderson

AIChE Regional Process Technology Conference
Galveston, Texas
October 8, 2010
 Outline
www.albemarle.com

ƒ FCC-PT process overview

ƒ Reaction zone concept
ƒ Catalyst system design guidelines
ƒ Catalyst deactivation causes
ƒ Summary & Conclusions

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 FCC Pre-Treatment Improves FCC
Product Quality and Operation www.albemarle.com

Vacuum Gas Oils (VGO/HVGO) Naphtha

Coker Gas Oils (CGO/HCGO) FCC Feed Distillate

Hydrotreater
Deasphalted Oils (DAO) (FCC-PT)
Light Olefins
Other Heavy Oils Fluid Catalytic Gasoline
Cracking Unit
Hydrogen (FCCU) Light Cycle Oil

Heavy Cycle / Slurry Oil

ƒ FCC Feed Hydrotreater generates feed to the FCC to improve

the quality by removing contaminants and adding H2
ƒ Generates some products directly; e.g., low S diesel
ƒ Fluid Catalytic Cracker uses acid-catalyzed cracking to break
heavy hydrocarbons down to gasoline and light cycle oils
ƒ Unit performs better on low contaminants, C/H ratio and N feed
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 FCC-PT Operates across a Wide
Range of Conditions www.albemarle.com

Feed is heavy with high S, N and C/H (i.e. high aromatics)

contents, metal contaminants (Ni, V, As, Si etc.), high
ConCarbon (0-4 wt.%) and particulates (FeS, coke fines)
Blend of VGO with lube extracts,
Feed
coker stocks, resid, DAOs, etc.
LHSV hr-1 0.5 - 1.2
ppH2 psi 600 - 2000
H2/Oil SCFB 1500 - 3000
Temperature °F 650 - 800 (EOR)
HDS Target % ≥ 80
HDN Target % ≥ 50

Different from ULSD and HC-PT (HDS/HDN conversion > 99%)

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 FCC-PT Catalyst Performance Is
Limited by Reaction Conditions www.albemarle.com

ƒ Even the most active catalysts only reach medium

conversion levels
ƒ Very difficult feeds treated at relatively low ppH2
ƒ Deactivation rate (due to coke, metals, sintering)
major determinant of cycle length
ƒ Temperature is too low to remove all N
ƒ N is the main HDS inhibitor
ƒ N inhibits aromatics hydrogenation
ƒ Actual conditions (ppH2, ppH2S, ppNH3 and
temperature) change throughout the reactor

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 Reaction Chemistry Changes at Each
Point in the Catalyst System www.albemarle.com

Temperature
Nitrogen
Sulfur

ppH2
NH3
H2S
Catalyst
System

6
 A Conceptual Reaction Zone Model:
FCC-PT Operates in Zones 1 and 2 www.albemarle.com

Zone 1 Zone 2 Zone 3

Sulfur content High Medium Low
Nitrogen content High Medium – Low Very Low
Zone 1 Polynuclear Aromatics High Medium – Low Zero
H2S in Gas 0 – Medium High Highest
NH3 in Gas 0 – Medium Medium High
H2 in Gas High Medium Medium – Low
Zone 2
Main HDS Reaction Direct Direct + Hydrog’n Hydrogenation
Main HDS Inhibitor H2S Organic Nitrogen –
Main HDN/HDA Reaction Hydrogenation Hydrogenation Hydrogenation
Zone 3 Main HDN/HDA Inhibitor Org. N, PNAs Org. N, PNAs PNAs
HDS Reaction Rate Fast Slow Fast
HDN/HDA Reaction Rate Very Slow Slow Slow-Medium

ƒ Reaction zones vary in length and position

ƒ ULSD and Hydrocracking PT operate in all 3 zones
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 Deactivation Cause-Effect Matrix
www.albemarle.com

Deactivation Impacts on
Primary Causes
Mechanism Performance

HDS ↓
Sintering / Agglomeration T↑ HDN ↓
HDA ↓

ppH2 ↓ HDS ↓
Coking of Active Sites T↑ HDN ↓↓
Feed C/H ↑ HDA ↓↓

HDS ↓↓
N N Feed N ↑
N N Organic N Inhibition
Feed EP ↑
HDN ↓
HDA ↓↓

HDS ↓↓
Pore Mouth Plugging Feed C/H ↑
HDN ↓↓
(by metals or coke) Feed EP ↑
HDA ↓↓

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 FCC-PT Catalyst System Design
www.albemarle.com

Feed + H2
ƒ Optimize overall performance by sequencing
catalysts with functionality selected to match
conditions and reactions in particular zones
Guard
of the reactor
Bed
ƒ Guard Bed:
ƒ Removes particulates (FeS, fines)
ƒ Removes metal poisons
ƒ Volume sufficient to protect the main bed catalyst
Main
Active
ƒ Main Bed:
Catalysts
Catalyst ƒ Design depends on unit’s operating strategy
ƒ Balance HDS, HDN and arosat objectives with
unit operating conditions / constraints
ƒ Optimize system via catalyst selection to achieve
required activity / stability in reaction zones
Products + H2
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 Guidelines for Robust System Design
www.albemarle.com

ƒ Avoid pressure drop build-up

ƒ Safely remove particulates
ƒ Manage highly reactive species
ƒ Mitigate impacts of inorganic poisons
ƒ Understand deposition mechanisms
ƒ Apply guard catalyst functionalities to control
ƒ Delay onset of coke deactivation
ƒ Operate as long as possible at T < arosat equilibrium point;
=> use high activity catalyst system
ƒ Minimize or mitigate PNAs in feed
ƒ Apply larger pore Main Bed active catalysts
ƒ More stability for coke and metals deactivation
ƒ Less diffusion resistance
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 Analysis of Different Catalyst Layers
for Coke and Metallic Contaminants www.albemarle.com

Coke Si Ni Fe V
ƒ Very significant catalyst
contamination in
30 commercial operation →
deactivation
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Contaminant Level (wt%)

VGO-demet (160 m2/g):

20 ƒ 10 wt% MoO3 → 2.7 at/nm2
ƒ 14 wt% C → 42 at/nm2
15 ƒ 8 wt% V2O5 → 3 at/nm2
ƒ 8 wt% SiO2 → 5 at/nm2
10 ƒ Deposited Ni ~ catalyst Ni
→ 2.3 at/nm2 total Ni
5
ƒ Coke higher at inlet and
outlet
0
ƒ Higher feed C/H @ inlet
Demet Layer 1 Layer 2 Layer 3 Layer 4 Layer 5
ƒ Higher Rx Temp @ outlet

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 Typical Contaminants Distribution in a
VGO Demet Catalyst: SEM-EDX www.albemarle.com

ƒ Low activity,
large MPD
ƒ Si near surface
ƒ Ni, V, Fe deposition
throughout the
particle
ƒ Recommended for
Guard Bed use

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 Typical Contaminants Distribution in a
Main Bed Catalyst: SEM-EDX www.albemarle.com

ƒ High activity,
moderate MPD
ƒ All contaminants
near surface
ƒ Can cause rapid
deactivation

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SEM-EDX near Extrudate Surface: Si Deposits
Form New Outer Layer on Main Bed Catalyst www.albemarle.com

ƒ Al defines the original

pellet boundary
ƒ Si originates from
17μm anti-foam agents
used by the refinery
ƒ Fe also in the Si layer
ƒ V on catalyst surface

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Crystal Analysis by STEM-EDX Mapping
Using Extrudate Sections: Ni-Sx-Asy Crystals www.albemarle.com

ƒ Analysis of
crystals in
spent catalyst
ƒ Mismatch of S,
Ni and As maps
ƒ Much broader
S distribution
ƒ More limited
As distribution

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 Ni-Sx-Asy Crystals in Close-up:
NiSx Adjacent to NiAsy and Ni-Sx-Asy www.albemarle.com

ƒ You can zoom in on specific crystals (maps, concentration

profiles) to learn more about their formation

S = red, As = blue, Ni = green

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 Ni-Sx-Asy Crystals in Close-up:
NiAsy between NiSx www.albemarle.com

S = red, As = blue, Ni = green

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 Ni-Sx-Asy Crystals in Close up:
Ni-Sx-Asy between NiSx www.albemarle.com

S = red, As = blue, Ni = green

Overall Results
ƒ Observe mainly separate NiAsy and NiSx crystals
with variable composition of NiSx
ƒ Only a few mixed Ni-Sx-Asy crystals
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 Example of Ni and V Contaminated Guard
Bed Catalyst: NixVySz Crystals in Close-up www.albemarle.com

ƒ Analysis of selected crystals in specific locations

ƒ Mismatch of Ni and V maps: NiSx vs. NixVySz

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 NixVySz Crystals in Close-up:
Mixed NixVySz Crystals www.albemarle.com

ƒ Selective orientations give similar Ni:V ratios of mixed

NixVySz crystals

V = Red, Ni = Green
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 NixVySz Crystals in Close-up:
Pure NiSx next to Mixed NixVySz Crystals www.albemarle.com

ƒ Other selective orientations give variable Ni:V ratios of

mixed NixVySz crystals

V = Red, Ni = Green
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 NixVySz Crystals in Close-up:
Pure NiSx next to NixVySz www.albemarle.com

ƒ Mostly observe NiSx and some NixVySz crystals

ƒ No pure VSx found: => NiSx needed to remove V from oil

V = Red, Ni = Green
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FCC-PT Catalyst Deactivation Recap
www.albemarle.com

ƒ Deactivation of FCC-PT catalysts is mainly due to coke

and metals deposition
ƒ Highest coke formation in reactor top and bottom
ƒ Large variety of metal deposits in guard bed and also
main bed catalyst if not sufficiently protected
ƒ NiSx required to remove V, As
ƒ Fe2O3 and FeS can not easily penetrate catalyst exterior
ƒ Si may form crust outside catalyst
ƒ In most cases, active phase sintering has minor effect

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 Optimum Catalyst System Design
Varies by Feedstock and Operations www.albemarle.com

ƒ Feedstock: VGO with 2.3 wt% S, 2300 ppm N, 3 ppm Ni+V, 4 ppm Si
ƒ Unit Pressure: 138 bar (2000 psi)
ƒ Catalyst System: KF 647 (Guard), KF 851 (Main)

30 730

25 720

SOR Operating Temp. (°F)

Predicted Cycle (months)

20 710

15 700

10 690

5 680

0 670
0% 10% 20% 30% 40% 50%
Guard Bed Catalyst (vol% reactor)
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 Overall Conclusions
www.albemarle.com

ƒ FCC-PT catalysts perform in a difficult reaction environment

ƒ Protection of main bed catalyst by effective use of guard
catalysts is essential to achieving long cycle length
ƒ Catalyst system design can be optimized for activity /
selectivity, coke resistance and H2 consumption
ƒ Good understanding of reactor zone chemistry and unit
capabilities / constraints crucial for maximizing overall
system performance / robustness
ƒ Enables most effective application of existing catalysts
ƒ Drives development of improved catalysts

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