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Selecting best RFCC Technology
ADID 2015
Carel Pouwels
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Outline
1. How do refiners select catalysts?
2. Testing refiners select different catalysts than non-testing
refiners
3. Changing trends in catalyst selection
4. Examples of trials
5. Summary and conclusions
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1.0
How do refiners select catalysts?
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Half of the FCC market is based on catalyst testing
Testing vs non-Testing Shares in Resid and VGO
24%
19%
29%
28%
Resid Testing
VGO Testing
VGO Non Testing
Resid Non Testing
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2.0
Testing refiners select different catalysts than non-testing refiners
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Short Catalyst intro
• Zeolite is most active component
• (Alumina) matrices are available in different flavors:
» Very active for cracking largest (resid) molecules
» Moderately/low cracking activity
» Metal encapsulation power (V, Ni, Fe, ….)
• The Matrix Myth “Matrices are considered to make more coke”:
» True: for “old” FCC designs with long residence time
» True: for laboratory tests
» False: for modern short contact time (R)FCC design
• Zeolite to Matrix ratio (Z/M) is important design parameter
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High Z/M cats are predominantly used by refiners who test but
non testers typically use low Z/M cats
Resid Applications
100%
90%
High Z/M
80%
Low Z/M
70%
60%
50%
40%
30%
20%
10%
0%
Testing

Non-Testing
Remarkable is also the significant presence of dedicated V-traps in the testing
segment, which we do not see in the non-testing segment
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Any catalyst lab study leads to unrealistic coke and slurry
yields and penalizes low Z/M catalysts
Slurry Benefit for low Z/M catalysts. wt%
2
FCC Unit
1
E-cat
D-cat
0
-2
-1
0
1
2
3
4
-1
-2
-3
-4
Coke penalty for low Z/M cats, wt%
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Differences in relative reaction rates due to hydrocarbon
partial pressure
• One of the key reactions is
Hydrogen Transfer, a bimolecular secondary reaction
» Strongly influences light olefins
• In ACE, C3= yields are
substantially higher when testing
the same catalyst from the
corresponding FCC unit
» HT reaction is much lower in
ACE
• Substantially lower hydrocarbon
partial pressure affects yields
and selectivities
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Details
• Valuable references with lots of data to substantiate this
phenomenon:
• AFPM 2013: AM-13-05, “Better Catalyst Evaluation Strategies for
Maximizing FCCU Margins”
• AFPM 2015: AM 15-29, “An innovative approach catapults refiners
to the next level in FCC catalyst selection”
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Consequence
“Testing” refiners are in general limited to
“good testing catalysts” while “non-testing”
refiners are open to all catalysts and select
the ones with “best proven performance in
the unit”
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3.0
Changing trends in catalyst selection
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Several testing refiners taking a novel approach for their
catalyst selection
• New approach taken by several refiners that previously selected
their catalyst based on testing
• This innovative approach opened the door to different catalyst
technologies and to full satisfaction of refiners
Case
Resid #1
Resid #2
VGO #1
Major refiner #1
Major refiner #2
Major refiner #3
Major refiner #4
Several refiners
Method
Trial
Trial
Trial
Correction
Correction
Correction
Correction
Trial
Comment
Slurry down, LCO up (Opposite of test at coke)
GLN and LPG olefins up (Opposite of test at coke)
Superior C3= (opposite of test)
Apply coke correction
Apply coke correction
Apply coke correction via excessive H2 yield
Apply coke correcton via matrix content
Stepwise increase of new cat technology in blend
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Testing customers expanding their catalyst options
• Several testing customers were caught in the “Loophole of
superior testing of high Z/M catalyst”
• Recognizing its limitation, they changed their catalyst selection
• Over last few years following trends have been seen:
» 17 refiners are now using back-to-back trials instead of deciding only on
basis of testing
» 6 refiners (of which 5 oil majors representing a multitude of FCC units)
apply (coke) corrections
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Trialing a new technology/catalyst supplier is considered a risk
How to avoid/minimize this?
• Decide on basis of references: feels risky, but can be safer when
applied correctly:
» New technology is proven in a reference unit:
» New technology performs equal or better than your incumbent catalyst
• Use New Technology first on trial basis
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Trial by selecting proven best catalyst on basis of references
• Reference: Unit and operation comparable to your (R)FCC unit
» Similar type of feed, similar type of operation mode (e.g. C3=), similar metal
levels:
• Proven catalyst means:
» Technology which has been used in the reference unit
» Whereby also your current catalyst (technology) has been used
• Best catalyst means:
» Whereby better (or at least equal) performance was obtained
» Based on key performance criteria for your refinery/FCC-economics:
• Max C3=
• Min Slurry
• Min dry gas
• Min Coke Selectivity (lowest dCoks, lowest RgT, lowest catcooler duty)
• Metals Tolerance:
• Catalyst Consumption (V, Na tolerance)
• Fe tolerance
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Use of solid reference for back-to-back trial minimizes risk
Only count references for your specific
application: “Resid to Propylene”
≠
“Reference for Resid” + “Reference for C3=“
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R&D’s invaluable role in catalyst selection
• Qualitative verification of performance claims seen in back-to-back
trials at reference units: hydrogen transfer, gasoline olefins, etc. –
“stop gate” to approve trials and minimize risks
• Determining correction/translation factors for all catalyst
(technologies) that have been used/trialed in your FCCU
• Qualitative verification of performance claims made by vendor for
reformulation within same/known catalyst technology
• Knowledge acquired by R&D to discuss with vendor possible
directions for further performance improvement
• Testing between different technologies without accounting for the
artifacts will not give meaningful results
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4.0
Examples of trials involving Albemarle’s AFX catalyst
in max propylene (resid) applications
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Refinery #1:
Successful start-up with Albemarle Catalyst
• Successful start-up of RFCC unit with
Albemarle’s cat processing heavy resid:
• Meeting target propylene yield at
defined operating conditions: 10.8 wt%
AFX
Competitor
Cat Cooler Duty, mmBtu/hr
» SG: 0.923
» CCR: 4.0 – 6.0 wt%
» Ni / V / Fe: 6 / 7 / 6 ppm
125
100
75
50
20.0
20.5
21.0
21.5
22.0
22.5
API º
• Refiner #1 decided to trial a max propylene catalyst of a competitor
• Trial unsuccessful, leading to higher coke (increased cat cooler duty), higher dry gas,
high slurry yield
• Refiner switched back to AFX catalyst
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Refinery #1:
AFX exhibits better coke selectivity and less slurry yield
• Lower C2• Higher C3=
• Better bottoms cracking, 0.5wt%
lower slurry
• Better coke selectivity
10%
AFX
Competitor
Slurry, wt%
9%
8%
7%
6%
0.1
0.2
0.3
Added Fe on E-cat, wt%
0.4
0.5
Feed Quality
API
SG
CCR
Sulfur
Operation Conditions
Feedrate
RxT
CFT
1st RGT
2nd RGT
Cat cooler steam
Equilibrium Catalyst
FST activity
Ni
V
Added Fe
Yields
DG
C3=
LPG
GLN
LCO
Slurry
Coke
Conv
Competitor
AFX
Normalized Conditions
º
21.8
21.8
0.923
0.923
wt%
4.1
4.1
wt%
0.36
0.36
ºC
ºC
ºC
ºC
Mt/h
Base
538
236
720
695
105
Base
538
236
716
688
105
wt%
ppm
ppm
ppm
67-69
2734
5271
0.23
67-69
2734
5271
0.23
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
4.6
8.8
25.4
45.8
8.6
7.8
7.9
83.6
4.4
9.5
26.9
45.2
8.4
7.3
7.9
84.3
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Refinery #2 processing HT-VGO
Albemarle’s max C3= catalyst replacing a competitor
• FCC unit processing 100% HT-VGO:
» SG: 0.91
5.0
» CCR: 0.1 wt%
Albemarle
» Very low Ni and V
Dry Gas, wt%
Competitor
4.5
4.0
3.5
530
535
540
545
550
555
RxT, ºC
 Albemarle’s max C3= catalyst successfully replaces a competitor catalyst
» Lower dry gas
» Higher propylene yield
» Lower bottoms yield
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Refinery #2:
Albemarle’s catalyst makes more C3= and less slurry
11.5
11.0
 Due to better dry gas
selectivity, the FCC unit could
operate at higher reactor outlet
temperature and lift the C3=
yield to higher levels
Albemarle
10.5
10.0
9.5
9.0
530
535
540
545
550
555
RxT, ºC
 Albemarle applied high AAI
technology to lower Hydrogen
Transfer and enhance C3=
 This technology also benefits better
slurry conversion
 Lab testing sometimes opposite of
unit
8
Albemarle
Competitor
7
Slurry, vol%
Propylene, wt%
Competitor
6
5
4
3
0.900
0.905
0.910
Feed SG
0.915
0.920
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Other trials:
AFX successes against latest competitive technologies
• Case #3: VGO application, operating at high severity:
»
»
»
»
HT-VGO (UOP-K=11.8), RxP>2.5 barg, RxT≥545 ⁰C
Higher C3=
Lower Slurry
Better coke selectivity
• Case #4: Very heavy resid application:
» SG=0.94, CCR=6~9 wt%, high asphalthene, Ni, Fe and Ca
» Higher C3=
» Better coke selectivity
• Case #5: Resid application:
»
»
»
»
SG=0.93, CCR=3~5 wt%
Higher C3=
Better coke selectivity
Lower slurry
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Other trials:
AFX successes against latest competitive technologies
• Case #6: Heavy resid application with high Fe feedstock
» Higher C3=
» Better coke selectivity
» Higher C4=
• Case #7: Very light feed application
»
»
»
»
»
Higher C3=
Better coke selectivity
Higher C4=
Better activity/stability
Unit results are superior to lab test winning catalyst
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Commercial back to back trials in summary
 Several refiners trialed a competitive technology
 In all cases several benefits were achieved for Albemarle’s max C3=
catalyst
 In all cases the refinery selected the Albemarle technology as preferred
 None of these cases were high in Zeolite to Matrix ratio
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What can go wrong in max C3= applications
Not meeting projected start-up yields
• Several cases are known of units starting up on non-Albemarle catalysts
not meeting the projected/desired performance:
» VGO unit #1:
» VGO unit #2:
» VGO unit #3:
» Resid unit #1:
» Resid unit #2:
severely lacking propylene yield
C3= yield met, but C4= too low, too low regenerator
temperature and too high catalyst consumption
lower C3= yield
lower C3= yield and higher catalyst consumption
C3= achieved but at lower feed rate and higher cat
consumption
• Often these issues are related to:
» Lack of knowledge and experience of the challenging application resulting in
poor catalyst design (most cases above use high Z/M technologies)
» Not optimal technology for max propylene and resid applications
» Too optimistic forecast
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5.0
Summary and Conclusions
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Summary and Conclusions
• Half of the FCC market is based on catalyst testing
» Those refiners typically select and apply high Z/M catalysts and are
limited to these type of catalysts only
• Non-testing refiners can apply all catalysts, but predominantly
select low Z/M catalysts
• Testing between different technologies without accounting for the
artifacts will not give meaningful results
» Develop and use translation/correction models after trialing new
technologies
» Use R&D tests to verify performance changes within catalyst technology
(catalyst reformulation)
• Selecting a new technology is recommended by use of references
• Using a new technology is recommended by use of back-to-back
trial to approve/reject further use in the future
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Summary and Conclusions, cont’d
• Sizable number of refiners have changed their catalyst selection to
back-to-back trials instead of using laboratory testing
• Select proven best catalyst on basis of references
» Reference: Unit and operation comparable to your (R)FCC unit with
identical application, for example “Resid to Propylene”
» Proven: Technology which has been used in the reference unit (and)
compared to your current catalyst (technology)
» Best: better (or at least equal) performance as your incumbent catalyst
• Many trials have been carried in max C3= (resid) applications
» Demonstrated a good method to assess the best catalyst technology
» Demonstrating AFX catalyst to perform superior
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