A5 Albemarle - Global Technology Forum

Increasing Revenues in Resid FCC
Carel Pouwels, Ken Bruno, Yen Yung, Eelko Brevoord
ERTC 2011
December 6, 2011

Content
Introduction
– Trends in RFCC
Introducing UPGRADER TM
– Albemarle’s Solutions for Processing More Residue
– Maximum upgrading at lowest Rare Earth
UPGRADER EXPERIENCE
– Cases of UPGRADER applications
Low Rare Earth Technology (LRT TM )
– Albemarle’s Solution for Processing More Residue at lowest Rare Earth
Summary and Conclusions
2

1.0
Introduction
Trends in Processing Residue in FCC
3

Crude Toward Heavier and Higher Sulfur
33
1.8
Gravity
Crude Gravity ( °API)
32
31
30
Sulfur
1.6
1.4
1.2
Sulfur (wt%)
29
1995 2000 2005 2010 2015 2020
1.0
Source: Hart World Refining and Fuels Service
4

Customer’s Requirements
Cost Reduction
– Cheaper (heavier) feeds: increased intake of resid
– Lower catalyst cost per ton feed: enhanced metal resistant catalysts
• Strong driver today: maximize upgrading at lowest RE2O3
Value Enhancement
– Increased conversion (activity)
– Upgrading to more valuable products
5

In resid applications, improved bottoms
conversion, lower coke or a balance between
both is usually most economic.
6

The Complex Chemistry of Coke Formation
Upgraded Products
Feed
Condensation
Alkylation
Cyclization
Aromatization
Polymerization
Hydrogen Transfer
Coke Precursors
Hydrogen Transfer
Dehydrogenation
Coke
7

Feed Coke and Metals Coke Dominate When Processing
Resid
70%
60%
50%
Delta Coke Contribution by Coke Type
Gas Oil
Resid
40%
30%
20%
10%
0%
Catalytic Stripping Feed Metals
8

Albemarle’s Matrices: Tunable for Heavy Molecules Pre-
Cracking and Low Coke Selectivity
Pre-cracking of heavy molecules by
matrix
Metals encapsulation/ trapping/
passivation by matrix
High Accessibility Structure
– Allows large heavy feed
molecules access to the active
sites
– Allows products to leave
without undergoing secondary
reactions
High pore volume and high cracking
activity
heavy
oil
binder
matrix
gasoline
zeolite
model
FCC catalyst model
9

Designing a Max Resid Catalyst
Requirements
– Good bottoms cracking for slurry conversion and low “feed coke”
– Metals tolerance for activity and low “metals coke”
– Optimize Hydrogen Transfer to limit “catalytic coke” and desired
balance between LPG and gasoline
– Open pore structure for low “stripping coke”
Design Parameters
– Matrix: Pre-cracking large molecules, metals tolerance, low hydrogen
transfer
– High Accessibility: high pre-cracking/low secondary reactions as
hydrogen transfer, condensation, polymerization, etc.
– Zeolite: activity, selectivity
– RE2O3: critical for resid
10

High accessibility, effective bottoms cracking matrix
with tunable metals resistance and coke selectivity
and greater zeolite activity and stability are key.
11

2.0
Introducing UPGRADER TM
Albemarle’s Solutions for Processing More Residue
12

Albemarle’s Solutions for Processing More Residue
UPGRADER TM : Lowest slurry in the industry
UPGRADER R+: Max bottoms conversion for delta coke limited operations
CORAL TM (SMR): Lowest coke selectivity
AFX TM : Maximum C3=
13

UPGRADER TM
Lowest Slurry in the Industry
Premium Resid Catalyst
– Utilizes improved manufacturing technology that permits higher AAI, better coke
selectivity, and expanded formulation window
• Succeeds previous OPAL TM catalyst family, known for its industry leading slurry
conversion
Applications:
– Resid feedstocks
– Cracking bottom of the barrel
– Diffusion constraint situations
– High V, Ni, Fe and/or Ca feeds
14

UPGRADER TM
Lowest Slurry in the Industry
Catalytic Features:
– Highest AAI in the industry
– Greater zeolite activity and stability
– Most effective bottoms cracking matrix with tunable metals tolerance and coke
selectivity
Potential Benefits:
– Lowest slurry in the industry
– Lower coke selectivity
– Max transportation fuels, tunable toward more gasoline or more LCO
– Increased throughput
– Increased olefinicity/octane
15

UPGRADER TM R+
Max Bottoms Conversion for Delta Coke Limited Operations
Application:
– Same as UPGRADER but where better coke selectivity is required in the unit
Features:
– Improved coke selectivity (more coke selective matrix) vs. UPGRADER
– Improved accessibility and V, Fe, Ca tolerance (vs. CORAL TM )
Potential Benefits:
– More resid processing than UPGRADER for delta coke limited units
– More bottoms destruction vs. CORAL
16

3.0
UPGRADER TM EXPERIENCE
Cases of UPGRADER Applications
17

UPGRADER TM
Refiner Needs to Reduce Bottoms of the Barrel
Resid FCC Unit:
– Specific Gravity: 0.90
– Sulfur: 0.6 wt%
– Conradson Carbon: 3.5 wt%
– Nitrogen: 700 ppm
Catalyst:
– Base catalyst: Competitive coke selective resid catalyst
– Activity: 64 w%
– Ni/V = 4000/6500 ppm
Refiners Objective:
– Bottoms cracking
18

UPGRADER TM
Massive Upgrading Potential of UPGRADER Demonstrated
6
Delta Yield, UPGRADER - COMPETITOR
60%
4
40%
Yield benefits, wt%
2
0
-2
20%
0%
-20%
Catalyst benefits, %
-4
-40%
-6
Gasoline LCO Slurry Conversion CAR AAI
-60%
19

UPGRADER TM
Massive Upgrading Potential of UPGRADER Demonstrated
Competitor
UPGRADER
Operating Conditions:
Feed Rate m³/h Base Base
Rx Outlet T °C 516 510
Rg Bed T °C 732 734
CTO 4.8 4.3
Delta Coke wt% 1.3 1.4
CAR mt/d 7.6 7.0
Ecat Quality:
Activity wt% 63.0 64.4
AAI Base + 50%
Yields:
Dry Gas (incl. H2S) wt% 2.6 2.4
LPG wt% 11.3 10.7
Propylene wt% 2.8 2.7
Total C4 wt% 7.6 7.2
Gasoline (C5-221C) wt% 41.4 44.0
LCO (221-400C) wt% 26.2 28.4
Slurry wt% 12.4 8.4
Coke wt% 6.0 6.1
Conversion wt% 61.4 63.2
* Normalized to equal feed quality, throughput and metals on Ecat
20

UPGRADER TM R+
Commercial Experience in UOP SBS Unit
Unit design: UOP SBS
Conditions: see table
Base catalyst: CORAL SMR (lowest
delta coke catalyst for resid)
Refiners objectives:
– Process more resid (improved
coke selectivity)
– Improved bottoms conversion
Feed Quality
Base case
Density g/cm 3 0.912
CCR wt% 1.5
Operating Conditions
Feed Rate, m3/h m 3 /h Base
RXT °C 522
RGT °C 716
Fresh cat additions t/d 4
CTO 6.6
E-cat
Activity wt% 70
Ni ppm 2132
V ppm 2539
21

UPGRADER TM R+
Combines Improved Bottoms Cracking with Low Coke Yield
UPGRADER R+ is a smashing success:
– enhanced metals resistance to improve coke selectivity: RgT decreased by 7 o C
– more effective bottoms cracking matrix
Leading to impressive conversion increase, slurry reduction and MON barrels uplift
CORAL SMR UPGRADER R+
Yields
Fuel Gas wt% Base -0.2
LPG wt% Base 2.0
C3= wt% Base 0.7
iC4= wt% Base 0.3
iC4 wt% Base 0.5
Gasoline wt% Base 1.5
LCO wt% Base 0.2
Slurry wt% Base -3.5
Coke wt% Base 0.1
Conversion wt% Base 3.3
Product Properties
C4 olefinicity Base 0.02
MON Base 1.0
22

4.0
Low Rare Earth Technology (LRT TM )
Albemarle’s Solutions for Processing More Residue at Lowest Rare Earth
23

Why do we Need Rare Earth in FCC Catalysts?
Why does Albemarle Need Less Rare Earth than Competition?
Zeolite is the most active component in FCC catalysts
This zeolite needs to be stabilized against steam deactivation at high regenerator
temperatures
Rare earth exchange is the most effective method to stabilize zeolite
However, there are also disadvantages from RE:
– Poorer coke selectivity
– Lower LPG olefins and gasoline octanes
It has always been Albemarle’s strategy to achieve optimum zeolite stability with less RE.
This way, negative effects of RE on performance are minimized.
Albemarle’s average rare earth content is the lowest
After the recent RE price increase, there is an appreciable reduction in catalyst costs due
to the lower RE on Albemarle catalysts.
– Example: 4 tpd, 1 wt% lower RE => $ 1.6 million per year
24

Albemarle offers a proven family of Low Rare Earth
Technology (LRT TM ) based Catalyst and Additives,
which have been supplied commercially.
25

Albemarle’s LRT Technology: Proven Family of Low Rare
Earth Technology Based on Catalysts and Additives
Makes use of a combination of proven technologies
– ADZT-200 zeolite treatment: Gives activity and RE-selectivity at lower RE levels
– High zeolite content
– High Silica to alumina (SAR) Y-zeolites: Extra stability!
– High matrix power (highest in industry)
– High accessibility: Better utilization of zeolite and matrix
– Metals tolerant and trapping technologies (non-RE-based)
We believe a minimum level of RE is required for optimum stability and cost/day
12
Delta Activity, wt%
10
8
6
4
2
0
2% Activity Increase with ADZT-200
Standard Zeolite
ADZT-200 Zeolite
First 0.5 – 0.7% rare earth oxide is optimal
0 1 2 3 4 5
RE2O3 on Catalyst, wt%
26

Albemarle’s LRT TM Solutions for Resid Applications
UPGRADER TM LRT:
CORAL TM LRT:
BCMT - 500 LRT:
Lowest slurry resid catalyst at low Rare Earth
Lowest coke resid catalyst at low Rare Earth
Low Rare Earth
Feed
Gas Oil
Residue
Desired
Output
Gasoline/Conversion
Maximum
Bottoms Cracking
AMBER TM
AMBER LRT TM
UPGRADER TM
UPGRADER LRT TM
LCO
Lowest Coke C3= Octane/C4=
GO-Ultra TM
GO LRT TM
UPGRADER R+ TM
CORAL TM
CORAL LRT TM
AMBER MD TM
UPGRADER MD
Octane/Olefins
AFX TM
AFX TM
ACTION TM
ACTION TM
27

UPGRADER LRT Increases Profitability in R2R Unit
Competitor UPGRADER TM LRT
Operating Conditions
Feed Rate BPD Base Base + 3000
Feed API 27.4 25.8
CCR, wt % 1.0 1.0
% VTB 14 17
Preheat Deg F 473 460
Riser Deg F 985 985
Regen Dense Deg F 1334 1323
Ecat Properties
Activity, wt % 65 65
RE2O3 wt % 2.30 0.85
Catalyst Addition Rate Base Base
Matrix Surface Area, m2/gm 37 83
AAI 2 7
FCCU Yields
C2 Minus, scfb 406 330
LPG, vol % 20.8 19.6
C3=/TC3 0.75 0.76
C4=/TC4 0.56 0.64
Gasoline, vol % 52.9 62.5
LCO, vol % 19.4 20.9
Slurry, vol % 16.4 8.2
Slurry API 12.9 4.2
Conversion, vol % 64.2 70.9
Profitability Base > $20 Million/year
RE2O3 = 0.85
– Maintains activity
– Superior performance
LRT Options employed:
– Higher matrix
– Higher AAI
Large yield benefits
– Above Critical AAI
Greater than $20MM/yr
increased profitability
28 28

5.0
Summary and Conclusions
29

UPGRADER TM and LRT TM
Summary and Conclusions
UPGRADER: The ultimate catalyst for converting resid
UPGRADER R+: For delta coke limited applications
– Advanced matrix components
– Highest matrix activity, as needed
– High AAI Technology
– Metals trapping technology, as needed
LRT products deliver maximum activity and performance per rare earth
– ADZT-200 Zeolites
– High zeolite loading, high SAR zeolites
– Optimized manufacturing technology
Albemarle’s average Rare Earth is the lowest
30