FCC Optimization

“Catalyst Design to Meet Market Dynamics”

Aruba Seminar - 2008

1
FCC Optimization

„ Optimization of the FCC:

z 60% of the process involves understanding the FCC potential
based on the quality of feed processed
z 30% of the process involves understanding FCC potential from
analysis of hardware, process variables, process limitations
z 10% of the process is developing a catalyst strategy to
compliment feed quality, hardware, process variables, and unit
limitations to maximize the financial objectives of the operation

10/27/2006 INTERNAL 2
Feed Quality

„ Conversion potential is set

by feed quality

„ Opportunity within the

bands is a function of FCC
hardware, process
variables and FCC
catalyst strategy

„ HPLC characterization is
a quality tool to provide
additional feed analysis

10/27/2006 INTERNAL 3
Unit Limitations

„ Wet Gas
„ Air Blower
„ Regenerator Temperatures
„ Fractionation
„ Light ends handling
„ Circulation
„ Product Quality (gasoline)
„ Environmental (not covered in this presentation)
z Opacity
– Microfines potential
z NOx
z SOx

10/27/2006 INTERNAL 4
Wet Gas Limitation:
Key Items to Evaluate

„ Feed Quality
z Understand contaminants (Ni, V, Sb/Ni) on dry gas production
„ Process Variables
z Riser Outlet Temperature
z Regenerator Bed Temperature
„ FCC Hardware
z Optimize total steam utilized (dispersion)
z Understand limits of feed nozzles, RTD
„ FCC Catalyst
z Rare Earth
z Metals Tolerance
z Activity Level / Coke Selectivity
z If you reduce severity you must be able to alter catalyst to reduce bottoms yield

10/27/2006 INTERNAL 5
Wet Gas Limitation:
Feed Quality

„ LPG increases with

hydrogen in the feed

„ The more crackable the

feed the higher conversion
potential

10/27/2006 INTERNAL 6
Wet Gas Limitation:
Process Variables

„ LPG increases with ROT

„ On the same catalyst

anything you do to
increase conversion will
more than likely increase
LPG and Wet Gas

10/27/2006 INTERNAL 7
Wet Gas Limitation:
Catalyst

„ Opportunity within the

bands is a function of FCC
hardware, process
variables and FCC
catalyst strategy

„ Directionally increases in
catalyst (FACT, TSA)
should increase
conversion

10/27/2006 INTERNAL 8
Wet Gas Limitation:
Catalyst

„ LPG decreases with

increase ReO

„ Z/M not a direct indication

of LPG production

10/27/2006 INTERNAL 9
Air Blower Limitation:
Key Items to Evaluate

„ Feed Quality
z Feed CCR, HPLC (coke making tendency of the feed)
„ Process Variables
z Riser Outlet Temperature
z Feed Preheat
z CO in flue gas (partial burn)
„ FCC Hardware
z Optimize total steam utilized (dispersion, stripper)
z Understand capabilities of feed nozzles, RTD, stripper
z Optimize Catalyst Cooler (more duty makes more coke)
„ FCC Catalyst
z Metals Tolerance (minimize coke from metals)
z Activity Level / Coke Selectivity
z If you reduce severity you must think about how you manage bottoms production

10/27/2006 INTERNAL 10
Riser Outlet Temperature

Lower Coke
Higher Coke

10/27/2006 INTERNAL 11
Air Blower Limitation:
Catalyst

„ Incremental Ni and V will

increase the catalyst
ability to produce
contaminant coke

„ Metals passivation
technology of catalyst can
alter this relationship

„ Sb can alter Ni ability to

produce coke

10/27/2006 INTERNAL 12
Air Blower Limitation:
Catalyst

„ Data shows higher Al2O3

catalysts produce higher
coke (Grace / Albemarle)

„ Increase in FACT will

increase coke

„ Key is to identify catalyst

that maximize activity per
unit of coke

10/27/2006 INTERNAL 13
DMS - Unique Structure Provides Unique
Benefits

„ DMS matrix provides

porosity for heavy
molecule diffusion and
cracking

„ Pre-cracking done with

the selective external
zeolite surface rather
than an amorphous non-
selective matrix

„ The combination of the

matrix and zeolite
technologies allows for a
high activity with low
coke selectivity
10/27/2006 INTERNAL 14
Regenerator Temperature Limitation:
Key Items to Evaluate

„ Feed Quality
z Understand CCR
„ Process Variables
z Riser Outlet Temperature (need to test how ROT impacts regen temp)
z Feed Preheat (lower preheat will reduce regen temperature)
z CO/CO2 for partial burn operation
„ FCC Hardware
z Optimize total steam utilized (dispersion, stripper)
z Understand limits of feed nozzles, RTD, stripper
z Optimize Catalyst Cooler (more duty makes more coke)
„ FCC Catalyst
z Metals Tolerance
z Activity Level / Coke Selectivity
z Promoter Usage

10/27/2006 INTERNAL 15
Regen Bed Temperature Limitation:
Catalyst

„ Higher Z/M catalyst can

assist in lowering delta
coke and lowering
regenerator bed
temperature

„ Pore Volume and/or

“Accessibility” does not
guarantee optimal delta
coke

10/27/2006 INTERNAL 16
Relative Size Of Resid Feed Molecules

Collection of Asphaltenes

Asphaltene

Multi-Ring Compound
Small Chain Alkane
0 25 50 100 200 (Angstroms)
Based on: Tissot and Welte; Petroleum Formation and Occurrence;
Springer-Verlag, 1978.
10/27/2006
05/08/2007 INTERNAL 17
Fractionator Limitation:
Key Items to Evaluate

„ Feed Quality
z Understand API, H2 content (conversion potential)
„ Process Variables
z Riser Outlet Temperature
„ FCC Hardware
z Need to understand where in the column are you limited and
force the converter to minimize that yield
„ FCC Catalyst
z Activity Level
z Selectivity Aspects of the catalyst (ReO, Z/M)

10/27/2006 INTERNAL 18
Circulation Limitation:
Key Items to Evaluate

„ Feed Quality
z Understand API, CCR
„ Process Variables
z Riser Outlet Temperature
z Feed Preheat
„ FCC Hardware
z Understand limits of feed nozzles, RTD, stripper
z Catalyst Cooler
z Flux (standpipes, stripper, slide valve dP)
„ FCC Catalyst
z Activity Level / Coke Selectivity (note lower coke may not be optimal)
z Catalyst Physical attributes (PSD, ABD)

10/27/2006 INTERNAL 19
Riser Outlet Temperature

Max Gasoline

Max LCO Max LPG

Min Dry Gas Min Bottoms

10/27/2006 INTERNAL 20
FCC Optimization

z Limitations
z Optimization opportunity
– ROT / dry gas / gas plant limitations
– Stripper/circulation/nozzles – understand coke selectivity
needs
– Regenerator – issues

10/27/2006 INTERNAL 21
Catalyst Design Process

„ Establish the bounds of the operation

z Evaluate feedstock quality to best understand regen dynamics
z Evaluate unit constraints
z Understand unit economic objectives
z Evaluate unit logistical constraints
„ Evaluate and understand the current catalyst management process
z What are the current catalyst and additive technologies utilized
z What is the design of the current FCC catalyst
„ Combine best-available catalyst technology to meet the specific needs of your unit objectives
„ Minimize local inventory to retain flexibility to alter FCC catalyst formulation
„ Minimize logistical issues with handling high levels of FCC catalyst and FCC additives

10/27/2006 INTERNAL 22
FCC Catalyst Optimization:
Dynamic Approach to Today’s Changing Feedstocks and Refinery
Economics

„ Unit Base Catalyst is Conservatively Designed for Poorest Feed Quality, not
most common operation.
„ Conversion Vs. Throughput

Ability to Independently Vary

z Zeolite Addition
z Metals Control
z Bottoms Upgrading Ability
z Gasoline vs. LCO Mode
z Gasoline / LPG Ratio

10/27/2006 INTERNAL 23
FCC Catalyst Optimization:
Catalyst Tools

„ Zeolite – Control Conversion / Upgrading to Gasoline

z Base Catalyst and Converter

„ Matrix – Control Bottoms Upgrading / LCO maximization

z Base Catalyst and Converter 55

„ Rare Earth Level – Balance Activity Control / Gasoline Selectivity / Delta Coke

„ ZSM-5 Zeolite – MOA to Control Gasoline to LPG conversion

z Refill alky unit during LCO maximization

„ Metals Tolerance
z Metals Traps / Catalyst Addition Rates
z Purchased Ecat – Metals, Activity, and Cost Control

10/27/2006 INTERNAL 24
How do you design a fresh catalyst
for varying feed quality?

Need for Gas Oil Based Design

Circulation
Wet Gas Limit
Frequency of processing

Fractionator (Upper)

Need for Resid Based Design

Base Catalyst
Design Point

Base Catalyst + High Activity

Air Limit
Regen Temp Limit
Wet Gas Limit
Feed ‘Heaviness’ (% Resid in Feed) Fractionator (Bot)

10/27/2006 INTERNAL 25
Case Study:
Base Catalyst + Converter

A B A B
From 12/1/2007 1/1/2008 2/1/2008 3/14/2008 6/1/2007 4/1/2007 1/1/2007 11/1/2006
To 1/1/2008 2/1/2008 3/14/2008 3/20/2008 8/1/2007 6/1/2007 4/1/2007 1/1/2007

Feedstock Flowrates and Properties Fresh Feed

Actual Feed Rate klpd 3119 2956 2494 2757 3068 3128 3219 3176
Feed Sulphur wt% 0.43 0.25 0.24 0.26 0.31 0.21 0.28 0.24
Feed CCR wt% 2.60 2.89 4.07 3.79 2.11 2.80 3.16 3.01
Actual Slurry Recycle Flow klpd 154 250 208 194 280 209 133 165

Reactor Conditions

Riser Outlet temperature °C 515 510 510 515 517 524 529 529
Feed Temperature °C 295 290 275 282 296 284 292 295
Catalyst Circulation TPH 10.23 9.63 10.22 10.68 11.20 10.87 9.55 12.33

10/27/2006 INTERNAL 26
Case Study:
Base Catalyst + Converter

A B A B
From 12/1/2007 1/1/2008 2/1/2008 3/14/2008 6/1/2007 4/1/2007 1/1/2007 11/1/2006
To 1/1/2008 2/1/2008 3/14/2008 3/20/2008 8/1/2007 6/1/2007 4/1/2007 1/1/2007

Regenerator Conditions

Regen Bed Temp below Feed °C 732 725 713 716 714 725 722 720
Average Regen Dilute Phase Temp °C 755 749 737 739 739 748 743 741

Catalyst Properties

Ecat MAT (wt%) wt% 74 73 69 70 73 72 71 70

Ecat TSA (m2/g) m2/g 135 130 110 115 115 112 114 113
Ecat Nickel (ppm) ppmw 1591 1762 2147 2146 1924 1950 2340 2245
Ecat Vanadium (ppm) ppmw 524 691 695 697 576 668 595 657
ZSM-% Addition Rate (wt%) wt% 0.00 0.00 0.00 0.00 0 0 0 0
ECAT Na (wt%) wt% 0.44 0.37 0.37 0.37 0.72 0.58 0.65 0.53
ECAT Fe (wt%) wt% 0.66 0.64 0.77 0.98 0.78 0.88 0.63 0.61

Base Catalyst Additions, tpd 4.00 4.40 6.00 7.00 6.50 6.50 6.00 6.00
Converter Additions, tpd 2.00 1.50 0.00 0.00

10/27/2006 INTERNAL 27
How do you design a fresh catalyst
for varying feed quality?

Need for Gas Oil Based Design

Circulation
Wet Gas Limit
Frequency of processing

Fractionator (Upper)

Need for Resid Based Design

Base Catalyst
Design Point

Base Catalyst + High Activity

Air Limit
Regen Temp Limit
Wet Gas Limit
Feed ‘Heaviness’ (% Resid in Feed) Fractionator (Bot)

10/27/2006 INTERNAL 28
Case Study:
Base Catalyst + Converter

A B A B
From 12/1/2007 1/1/2008 2/1/2008 3/14/2008 6/1/2007 4/1/2007 1/1/2007 11/1/2006
To 1/1/2008 2/1/2008 3/14/2008 3/20/2008 8/1/2007 6/1/2007 4/1/2007 1/1/2007

Reactor Yields

H2 wt% 0.10 0.05 0.05 0.07 0.14 0.09 0.08 0.08

Total H2-C2 (wt%) wt% 2.83 2.83 3.00 3.05 2.76 2.94 2.76 2.78
C3= wt% 4.44 4.19 4.20 4.57 3.82 4.16 3.97 3.95
Total C3s wt% 6.37 5.90 5.67 6.33 5.64 6.15 5.92 5.77
C4= wt% 4.63 5.29 5.38 5.70 3.25 4.66 4.39 4.42
Total C4s wt% 9.97 8.82 8.82 9.60 8.83 9.19 8.63 8.41
Total C3s+C4s wt% 16.34 14.72 14.49 15.92 14.47 15.33 14.55 14.18
LCN C5-221C wt% 49.77 47.62 44.72 48.78 43.42 42.61 41.84 41.30
LCCO 221C-350C wt% 19.46 19.43 20.50 16.80 21.07 19.15 19.53 19.94
DCO 350C + wt% 5.44 8.65 9.83 7.74 11.82 13.20 14.57 14.37
Coke wt% 6.16 6.62 7.34 7.57 6.34 6.76 6.74 7.14
Conversion wt% 75.10 71.92 69.67 75.47 67.11 67.65 65.90 66.25

10/27/2006 INTERNAL 29
How do you design a fresh cat / ecat
system for varying feed quality?

Circulation
Need for High Activity Based Design
Wet Gas Limit
ECAT added for control of metals,
Frequency of processing

Fractionator (Upper)
manage delta coke and minimize costs

Highest ECAT
additions
Base Catalyst Design Point /
High Activity Base Catalyst
Air Limit
Regen Temp Limit
Wet Gas Limit
Feed ‘Heaviness’ (% Resid in Feed) Fractionator (Bot)

10/27/2006 INTERNAL 30
Effect of Catalyst Addition Rate on Unit
Change Out Rate

Unit Changeout as a Function of Turnover Rate

¾ P=1-e(-sft)
100%

90%
s=0.10

80%
s=0.08
„ 2% Turnover Rate Completes 36%
70%
s=0.05
Change out in 30 days.
Unit Changeout, %

60%
„ 5% Turnover Rate Completes 50%
50%
s=0.03
Change out in 19 days.
40%
s=0.02

30% „ 10% Turnover Rate Allows 50% Unit

20% Change out in 9 days.
10%

0%
Time, Days

„ Basis: f=0.75

10/27/2006 INTERNAL 31
Y= (Yo*s)/(s+k)
Catalyst Activity Calculation

Y – Unit MAT Yo – Fresh s – Turnover K – Deactivation Catalyst Additions,

Catalyst MAT Rate Coefficient TPD
70 81.25 0.556 .047 20

70 85 0.033 .047 12

70 80 0.066 .047 24

70 79 .077 .047 28

„ Unit Activity can be Maintained by Varying Fresh Catalyst

Activity and Addition Rate.

„ Basis: 360 ton Inventory

10/27/2006 INTERNAL 32
Case Study:
Use of Purchased ECAT

„ Refinery Changes Feed Quality with Objective of Maintaining

Feedrate and Catalyst Activity.
„ Basis: Evaluate different Fresh Catalysts with and without the use
of purchased ecat

10/27/2006 INTERNAL 33
Case Study:
Use of Purchased ECAT

„ Basis: Vary Catalyst Additions and Activity to:

z Maintain 70 MAT in Unit
z Maintain 2500 ppm Ni and 2500 ppm V in Unit.
z 85 MAT Fresh Catalyst
z 75 MAT Ecat with 500 ppm Ni; 1000 ppm V

Y – Unit MAT Yo – Fresh S – Unit K – Deactivation Catalyst

Catalyst MAT Turnover Rate Coefficient Additions – TPD
70 85 0.0333 .047 12

70 81.25 0.0556 .047 20

70 80 0.066 .047 24

70 79 0.077 .047 28

10/27/2006 INTERNAL 34
Case Study:
Use of Purchased ECAT

Cat Adds, TPD Fresh Adds, Ecat Adds, TPD Feed Ni, ppm Feed V, ppm
TPD
12 12 0 3.1 3.1

20 10 10 4.7 4.2

24 9 15 5.5 4.7

28 8 20 6.3 5.2

Cat Adds, TPD Days for 50% % Turnover in 10 % Turnover in 30

Turnover Days Days
12 28 22 53

20 17 34 71

24 14 39 78

28 12 44 83

10/27/2006 INTERNAL 35
Case Study:
Use of Purchased ECAT

Catalyst Endurance Jade Jade w/Ecat Flex Tec Flex Tec

+ Ecat
Date 3/15/03 11/29/02 10/11/02 5/22/02 8/31/01
9/29/03 3/15/03 11/22/02 10/4/02 5/20/02
FACT WT% 68.50 68.93 65.42 68.37 66.39
SA M2/G 118 103 109 121 116
MSA M2/G 38 58 45 40 38
Ni PPM 2056 1746 2317 2238 2931
V PPM 3190 2795 3363 2742 2895
Na WT% 0.32 0.38 0.40 0.37 0.34
Al2O3 WT% 38.65 51.77 44.53 38.99 38.31
REO WT% 2.03 2.02 1.96 2.06 2.15
ABD G/CC 0.85 0.88 0.87 0.86 0.87
PV CC/G 0.34 0.33 0.33 0.34 0.34
Fe WT% 0.57 0.43 0.52 0.56 0.44
FCF WT/WT 1.39 1.74 1.69 1.17 1.32
FGF VOL 0.94 0.91 0.93 0.93 0.92

0-40 WT% 1 2 2 2 4
0-45 WT% 4 5 6 6 8
0-80 WT% 49 46 54 54 56
0-105 WT% 77 71 79 81 81
APS MICR 80 83 78 77 76
SB/NI N/A 0.18 0.18 0.23 0.22 0.24

10/27/2006 INTERNAL 36
Case Study:
Use of Purchased ECAT

Catalyst Endurance Jade Jade w/Ecat Flex Tec Flex Tec

+ Ecat
Date 3/15/03 11/29/02 10/11/02 5/22/02 8/31/01
9/29/03 3/15/03 11/22/02 10/4/02 5/20/02

DG. WT% 2.42 2.66 2.51 2.33 2.24

GASO. WT% 48.0 47.9 46.3 48.7 47.6
LCO. WT% 18.9 18.6 20.0 18.7 19.5
BOT. WT% 12.60 12.56 14.54 12.93 14.22
COKE. WT% 3.30 4.21 3.53 2.75 2.86
Bot + Coke WT% 15.90 16.77 18.07 15.68 17.08
H2/C1. RATIO 5.0 4.2 5.1 4.4 5.7
C3=/T. RATIO 0.83 0.81 0.83 0.83 0.84
C4=/T. RATIO 0.63 0.62 0.66 0.63 0.64

10/27/2006 INTERNAL 37
How do you design a fresh cat / ecat
system for LCO / Gasoline optimization?

Circulation Limit High Z/M, High ReO, High

Wet Gas Limit Activity
Fractionator Limit
Frequency of processing

Low Z/M, Low ReO, Moderate

Activity, ZSM-5 to fill wet gas

ECAT used
for cost
minimization
Base Catalyst Design Point
Air Limit
Bottoms Limit

Economics Favoring LCO Production

10/27/2006 INTERNAL 38
Benefits of Customized FCC Solutions

„ Combine best-available catalyst / additive technologies to provide

flexibility to meet the specific needs of your unit objectives
„ Minimize local inventory to retain flexibility to alter FCC catalyst
formulation
„ Minimize logistical issues with handling high levels of FCC catalyst
and FCC additives
„ Leverage total industry to obtain highest potential catalyst
technology solution`
„ Opportunity to manage costs
„ Insulate refiner locations from any supply side disruption

10/27/2006 INTERNAL 39