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Optimizing & Troubleshooting


the FCC Regenerator for
Reduced Emissions

Ray Fletcher & Martin Evans


March 2010

1 5/3/2010
Overview
z Introduction
z Particulate
a t cu ate e
emissions:
ss o s
– Catalyst attrition
– Cyclone integrity
z Afterburn
– Analysis & control
z Gaseous emissions
– Control of SOx emissions
– Control of NOx emissions
z Conclusion

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NPRA Annual Meeting – March 2010
www.intercatinc.com
Introduction
z Substantial experience has been gained during
the last 68+ years related to FCC regenerator
operations
z Effective troubleshooting is based upon a solid
set of baseline data taken during normal
operations
z Selective use of additives will enable the refiner
to enhance the performance of the regenerator
z Refer to reference section of associated paper
for key landmark papers related to regenerator
troubleshooting

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®
NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Overview
z Introduction
z Particulate
a t cu ate e
emissions:
ss o s
– Catalyst attrition
– Cyclone integrity
z Afterburn
– Analysis & control
z Gaseous emissions
– Control of SOx emissions
– Control of NOx emissions
z Conclusion

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NPRA Annual Meeting – March 2010
www.intercatinc.com
Attrition in Regenerators
Particle attrition at grids
z Two primary sources of attrition: with back eddy
– Continuous & minor:
z Submerged jet attrition at the grid
z Attrition in cyclones
z Attrition at load line elbows
– Abnormal & substantial:
z Improperly designed, eroded, or missing orifices in
steam lines
z Excessive velocities through air grid
z High turbulence caused by a broken air grid
z High catalyst velocities through slide valves
z Most units will have a low level of attrition
occurring continuously
Air
– Baseline essential

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Attrition in FCC Regenerators
z Procedure for monitoring catalyst
attrition:
– Capture & analyze fines samples regularly
z 3rd stage separator or 1st stage ESP bin
– Plot wt% capture vs. PSD
z Normal distribution:
– One primary peak at 20-30 μ
– One attrition peak at 0-5 μ
– One “breakage” peak at 10-15 μ
z Attrition source present:
– Primaryy ppeak shifted to lower p
particle size
& reduced in magnitude
– Attrition peak increases & dominates

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Cyclone Integrity
z Mechanically related problems:
– Broken welds
– Holes from erosion or high stress tears in
the cyclone or dipleg
– Dipleg valves which do not operate
– Dipleg valves which do not close because of
bent or lost closure plates
z Operationally related issues
– Excessive mass flows in cyclones & diplegs
– Insufficient dipleg length

(Conceptual example)
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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Dipleg Pressure Balance
z Knowledge of cyclone dipleg levels is critical
– Minimum distance of catalyst level to cyclone
vortex is approximately 600 mm (24 inches)
– Increases in charge rate can increase required
dipleg level beyond this minimum
– Result: catalyst attrition, erosion in cyclone cones
& hoppers, entrainment
z Higher catalyst levels occur in secondary
cyclones lead to entrainment losses
– Plot cyclone dipleg heights vs. catalyst losses to
determine unit specific critical dipleg level ρdl
hdl
z Typical dipleg & bed densities:
ρbed
– Primary dipleg: 480 kg/m3 (30 lb/ft3)
hbed
– Secondary dipleg: 320 kg/m3 (20 lb/ft3)
– Bed density: 800 kg/m3 (50 lb/ft3)

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Troubleshooting Cyclones
z Primary cyclone hole
– A secondaryy ppeak is observed to the right
g of
the primary peak
z Positioned at >60 μ
– The attrition & breakage peaks continue to
be present

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Troubleshooting Cyclones
z Secondary cyclone hole
– A secondaryy ppeak is observed to the right
g of
the primary peak
z Positioned at 45-50 μ
– The attrition & breakage peaks disappear
z Flooded cyclones
– Primary peak shifts to the right of a typical
unit
– The attrition & breakage peaks continue to
be present

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®
NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Overview
z Introduction
z Particulate
a t cu ate e
emissions:
ss o s
– Catalyst attrition
– Cyclone integrity
z Afterburn
– Analysis & control
z Gaseous emissions
– Control of SOx emissions
– Control of NOx emissions
z Conclusion

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NPRA Annual Meeting – March 2010
www.intercatinc.com
Regenerator Afterburning
z Afterburning is any increase in flue gas
temperature after leaving the dense bed
– May occur in dilute phase, cyclones, or flue gas
– Little catalyst present to absorb heat of combustion
– May limit throughput or feedstock flexibility
– May result in serious damage to internals leading
to premature shutdown & costly repairs
z Two types of afterburn observed:
– Kinetic limited afterburn
z Due to insufficient regenerator bed residence time
for complete combustion
Source: Jack Wilcox,, RPS
– Afterburn
Aft b induced
i d dbby poor air
i &/
&/or catalyst
t l t
distribution
z Frequently due to inherent design features &/or air
grid mechanical failures
g

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Kinetic Limited Afterburning
z Characteristics:
– Well dispersed afterburn across regenerator
cross section
– High superficial velocities
– Low bed levels
– Low bed tempertures
z Solutions:
– Raise bed level
– Increase bed temperatures
z Add CO Promoter
z Thermodynamically limited units generally
respond well to platinum

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Distribution Induced Afterburning
z Characterized by localized afterburning O2 rich CO rich O2 rich

z Induced by
yppoor air &/or catalyst
y distribution
– Due to mixing of CO & O2 rich zones above bed
– Responds less well to CO Promoter
z Monitor hotspotp temp p as Pt concentration increases
z Hotspot temperature will drop until O2 is fully
consumed in effected region
z Continued additions after temperature fails to drop
O2 rich CO rich
has little effect on regionalized afterburn
z NOx emissions will continue to increase
– A normally well behaved unit which begins to
afterburn together
g with a change
g in losses or
equilibrium PSD indicates air grid damage
z Suspected maldistribution may be confirmed
using a portable gas analyzer
Source: J.W. Wilson, AM-03-44

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Gas Analyzer Verification
z Portable gas analyzers are Catalyst side-entry

effective at confirming #1
CL

maldistribution
330°

z Typical equipment used:


– Reaction Mix Sample (RMS)
probe
– Mott filter element used to
remove catalyst fines from the
gas stream

150°
Catalyst
190°
P1 withdrawal
CJI #2
#3

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Overview
z Introduction
z Particulate
a t cu ate e
emissions:
ss o s
– Catalyst attrition
– Cyclone integrity
z Afterburn
– Analysis & control
z Gaseous emissions
– Control of SOx emissions
– Control of NOx emissions
z Conclusion

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NPRA Annual Meeting – March 2010
www.intercatinc.com
Controlling SOx: Full Combustion
z Feedstock effect
– About 10% emitted as SOx ((range:
g 5-35%))
z Improve SOx additive efficiency:
– Drive SO2 to SO3 equilibrium towards SO3
z Increase excess O2 ((up
p to ~2%))
z Reduce bed temperature
z Increase regenerator pressure
z Use Pt based CO promoter
– Enhance additive regeneration
z Increase cat circulation rate
z Factors reducing additive efficiency:
– High catalyst losses
– Large regenerator inventories
– Poor stripper efficiencies
– High Fe on equilibrium catalyst Total elimination of SOx emissions is achievable

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Controlling SOx: Partial Combustion
z SOx additives in partial burn: •Sulfur Species Data from European FCC @ 7% CO

– Majority
j y of S in reduced form
z COS, CS2,H2S
– Oxidation of S→SO2→SO3 limiting step
– Tailored oxidation component required
for maximum additive effectiveness
z Measure SO2 is flue gas prior to using
additives in partial burn
– Approximately 30% of S in oxidized state
z Partial burn guidelines:
– There is a practical upper limit
z Monitor SOx concentration in flue gas
Deep SOx reductions in partial burn are feasible
upstream of CO Boiler thru trial
– Monitor regenerator CO-to-CO2 ratio as
additive concentration increases
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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Controlling NOx Emissions
z NOx formation: Fluegas NOx vs Excess O2
– ~10% of N in coke emitted as NOx 200

NOx Emissions  (ppm)
– Excess O2 is the most significant operating 150

variable affecting NOx emissions 100

z Maldistribution of air & catalyst


y leads to 50

high NOx emissions


0.6 0.8 1.0 1.2 1.4

Excess Oxygen (ppm)

– Additive efficiency is highly unit specific


z NOx reducingg additives are effective in
full combustion
– There is an effective unit specific maximum
concentration
z Exceeding this maximum will have no effect
or may actually increase NOx

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Designing for Low NOx Emissions
z Control of air-to-catalyst mixing critical to
low NOx emissions
– Combustor type regenerators with superior air-
to-catalyst mixing control NOx emissions well
z Bubbling bed regenerators may be
improved for reduced emissions:
– Ensure counter current operation
– Distribute spent catalyst uniformly across the Courtesy: KBR

top of the regenerator bed


– Inject combustion air uniformly across cross
section of regenerator
z Additives are effective
Additi ff ti forf further
f th
reductions as needed

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Troubleshooting NOx Emissions

z Detecting maldistribution via comparison of cyclone delta temps


– Calculate & plot NOx emissions vs vs. delta temps for each cyclone pair
combination
– Look for obvious pattern differences
– Confirm with multivariable linear regressions
– Use regression analyses plus time plots identify likely root cause & timing
– Perform step tests in unit to confirm suspected process variables

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NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
CO Promotion & NOx Emissions
z NOx emissions increase as platinum
content increases
– Simultaneous control of afterburn & NOx
emissions is possible via non-Pt promoters
– Fully commercialized solution
z Utilize best available additive loader
technology for optimum performance
– Reliable additive injection is essential
– Intercat offers free loader usage for all its
customers

Example of enhanced additive


effectiveness due to improved loader
reliability
22
®
NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
Overview
z Introduction
z Particulate
a t cu ate e
emissions:
ss o s
– Catalyst attrition
– Cyclone integrity
z Afterburn
– Analysis & control
z Gaseous emissions
– Control of SOx emissions
– Control of NOx emissions
z Conclusion

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NPRA Annual Meeting – March 2010
www.intercatinc.com
Conclusion
z Advanced troubleshooting techniques will
enable the process engineer to effectively
monitor, troubleshoot, & optimize the FCC
regenerator
– A solid base case taken during normal operations is
f d
fundamental
t l tto swift
ift troubleshooting
t bl h ti

z Intercat has developed a substantial base of


“hands on” regenerator troubleshooting &
optimization expertise
– Refinery support available upon request

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®
NPRA Annual Meeting – March 2010
5/3/2010 www.intercatinc.com
®

www.intercatinc.com

Optimizing & Troubleshooting


the FCC Regenerator for
Reduced Emissions
Ray Fletcher & Martin Evans
March 2010

25 5/3/2010