Cat Cracker Seminar

August 24-25, 2010

InterContinental Hotel
Houston, TX

CAT-10-110 Failure Mechanism for FCC Cyclones

Presented By:

Mike Maholland
FCC Process Specialist
Chevron Global
Manufacturing
Salt Lake City, UT

Doug McAulay
Principal Mechanical
Engineer
BP Refining Technology
Carson, CA

National Petrochemical & Refiners Association 1667 K Street, NW 202.457.0480 voice

Suite 700 202.429.7726 fax
Washington, DC www.npra.org
20036.3896
This paper has been reproduced for the author or authors as a courtesy by the National
Petrochemical & Refiners Association. Publication of this paper does not signify that the
contents necessarily reflect the opinions of the NPRA, its officers, directors, members, or staff.
Requests for authorization to quote or use the contents should be addressed directly to the
author(s)
 1. Erosion
2. Flow Restriction in Diplegs
3. Dipleg Gas Leakage
4. Metallurgical Degradation
5. Refractory and Hexmesh Degradation

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 Cyclone Design Operation and Monitoring
• Best Practice Design Guidelines • Process Monitoring
Developed From: • Erosion Rate Prediction Tool
• Past experience
• Design & Engineering Companies
• Cyclone Vendors
• PSRI
• Other industry sources

Inspections and
Maintenance
Lessons Learned Improvements • Planned and Expected
• No Surprises

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 ` Pressure Drop Across Cyclones
` Cyclone Pressure Balance
◦ To monitor level of catalyst in diplegs
◦ Ensure adequate dipleg seal and dipleg margin
` Cyclone Temperatures
◦ Especially important in regenerator cyclones where high temperature
afterburn may be a problem
` Inlet and Outlet Cyclone Velocities
◦ Erosion rate is a power function of velocity
` Entrainment Rate
` Catalyst Properties
◦ Especially APS and PSD
` Catalyst Balance Around the Unit
` Cyclone Efficiencies
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 ` Fluid Bed System Simulation (FBSS) Software
by PSRI
◦ Can be used to model and evaluate many process conditions
◦ Set up for each FCCU in your system
◦ Can be used to troubleshoot cyclone operating problems
` Predictive Cyclone Erosion Model
◦ Predictive tool to estimate the extent of refractory loss by erosion
and estimate the remaining life of cyclone
◦ Requires an initial set up and calibration, then confirmation (and
recalibration if necessary) at each unit shutdown and inspection
◦ PSRI plans to develop a tool as part of their research on cyclones

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 ` Inlet Ducts
` Wall Opposite of
Barrel Inlets
` Outlet Tubes
` Crossover Duct
o
` 2 Cone
o
` 2 Dustbowl
o
` 2 Upper Dipleg

Source: Buell

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 Source: PSRI

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• Lower dustbowl and
upper dipleg area is
where most through-
the-wall holes have
been reported
• Contributing Factors:
• Short Cyclone L/D
• High Velocity
• High Number of
Spins
• Long Vortex
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 ` Encapsulate the hopper
cone and upper dipleg with
a refractory-lined steel shell Steel Plate
` Ensure that: Encasement
◦ The encasement extends
adequately above and
below the damaged area Refractory
Fill
◦ Is adequately vented for
refractory dry out
◦ The cyclone support system
can support the added
weight

Damaged Area

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• Allows for
operation until
next scheduled
turnaround
when cyclones
can be replaced

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 ` Diplegs can become plugged with coke, refractory
or catalyst
` Catalyst plug in dipleg commonly due to:
◦ Startup Conditions
x Low temperatures during initial phases of startup
x Wet steam
x Wet catalyst
◦ Low secondary cyclone dipleg mass flux
x Catalyst can slump and bridge
◦ Inoperable dipleg valve
x Valve stuck closed preventing catalyst from exiting dipleg

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 ` Valves can become
stuck open or closed
by:
◦ Mechanical malfunction
(e.g., hinge, ring or pin)
◦ Coke
◦ Debris
◦ Incorrect or missing
counterweights on
counterweighted flapper
valves

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 ` Can occur in negative pressure cyclones
` Occurs more typically in secondary cyclones
because of low mass flux
` Upward flow of gases can cause erosion of dipleg
(lower secondary diplegs are typically unlined)
` Can re-entrain catalyst and increase erosion rate
in the cyclone dustbowl
` Reduces cyclone efficiency
` Result of poor sealing dipleg valves

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` Lap patch placed
around lower
dipleg where
internal erosion
occurred
` Adjusted seal
gap on flapper
valve
` Plan to replace
dipleg and valve
next T/A

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 Material Degradation Effect on
Remaining Cyclone Life

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 Material Degradation Effect on
Remaining Cyclone Life
` Background
` Metallic Degradation.
` Refractory Degradation.
` Evaluation

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 Material Degradation Effect on
Remaining Cyclone Life
` Background
◦ Over the years, scores of refineries with FCCU’s have faced the
dilemma; do we repair or replace?
◦ Where operational temperatures exceed 1200°F (650°C) - Austenitic
(typically Type 304H) Stainless Steels have traditionally been used.
◦ This material is selected as a cost effective solution, given the
requirement for oxidation resistance, strength and creep property
requirements based on the operational temperatures involved with
FCCU service.
◦ Typically cyclone replacement is for technology or process reasons.

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 Metallurgical Damage Mechanisms

` Sensitization:
All 304 materials will be in the sensitized condition after
exposure to regeneration temperatures and most
refiners tend to cope with this condition by keeping
materials free from excessive moisture during outages.

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 Metallurgical Damage Mechanisms

` Erosion:
Erosion of the metallic portion of the cyclones is usually
caused by high velocity.
◦ Poor distribution in Regenerator
◦ Loss of refractory
◦ External source of local high velocity such as dome steam
◦ Increase in unit throughput
◦ Poor design

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 Metallurgical Damage Mechanisms

` Sigma formation:
As a result of high temperature exposure the formation of a
metallurgical phase known as sigma phase can result in a
loss of fracture toughness in stainless steels.
◦ More prevalent in weld metal
◦ Occurs relatively quickly
◦ Steel chemistry, cold work and thermal processing effect sigma
formation
◦ Failures usually occur below the critical temperature

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 Metallurgical Damage Mechanisms

` Carburization:
◦ Can occur within a few weeks at normal operating temperatures if
carburising conditions exist
◦ The stainless steel becomes brittle
◦ Weld repair becomes more difficult or not possible depending on
degree of carburisation
◦ Detected by the stainless steel becoming magnetic and visibly by the
black, soot like appearance

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 Metallurgical Damage Mechanisms

` Creep:
At high temperatures, metal components can slowly and
continuously deform under load below the yield stress.
This time dependent deformation of stressed components
is known as creep.
◦ Using the standard creep life calculation method of API RP 530 (the
Larson-Miller Parameter technique, which tends to be rather
conservative), a creep life table for various temperatures and
stresses is shown below:

Note: Creep life calculations show large data scatter – the multi-digit
significant figures in the table are presented only for comparison
purposes

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 Metallurgical Damage Mechanisms
Creep life table
Temperature (F) Design Case -- Case 2 -- Case 3 --
Estimated Creep Estimated Creep Estimated Creep
Life @ 1.8 ksi Life @ 3.6 ksi Life @ 5.4 ksi
1300 F (704°C) 1877 years 48.1 years 5.2 years

1325 F 917 years 24.8 years 2.8 years

1350 F 457 years 13.0 years 1.5 years

1375 F 232 years 6.9 years 0.82 year

1400 F 120 years 3.7 years 0.56 year

1425 F 63 years 2.1 years 0.26 year

1500 F 10 years 0.4 year 0.05 year

1600 F (871°C) 1.1 years 0.05 year 0.01 year

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 Metallurgical Damage Mechanisms

` Creep (continued):
◦ This is important in that if cyclone wall or hanger thickness is reduced
by erosion, for example, the actual stresses increase, and the creep
life decreases. Erosion thinning, stress concentrations at notches or
cracks, and sharp changes in cross section all locally increase the
applied stress, and therefore are areas to look for during an
inspection.
◦ Temperature Excursions

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 Metallurgical Damage Mechanisms

` Weldability:
Weldability is also a major factor in the decision making
process for optimal, cost effective decision making with
regards to effective repair or replacement.
◦ Sigma formation
◦ Carburisation
◦ Section Thickness
◦ Consumable
◦ Pre-heat
◦ Cooling rates

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 Material Degradation Effect on
Remaining Cyclone Life

Refractory

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 Refractory Damage Mechanisms

` Erosion
` Thermal Cycling
` Corrosion

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 Refractory Damage Mechanisms

` Erosion:
◦ High Velocity
◦ High particulate loading
x High superficial velocity
x Poor performance of Primary cyclones

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 Refractory Damage Mechanisms

` Thermal Cycling:
◦ Emergency shutdowns
◦ Heat-up or Cool-down outside of recommended procedure

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 Refractory Damage Mechanisms

` Corrosion:
◦ Sulfur in feed
◦ Regenerator performance
x Afterburn
x Coke removal
◦ Refractory installation
◦ Refractory chemistry

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 Hexmesh Failure Description
Corrosion Case Study

` Hexmesh linings have failed prematurely in many

refineries.
` BP Rotterdam FCC was used as a case study
` Failures are primarily due to hot corrosion of the stainless
anchor system, welds and cyclone wall
◦ Penetration rate is on the order of 2 to 20 mpy (0.05 to
0.5 mm/y)
` Failures are localized to confined spaces
◦ Crevices between refractory and anchor ligaments
◦ Gaps between cyclone wall and refractory

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 Hexmesh Failure Description

flue gas side unattacked wall plate side attacked

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 Hexmesh Failure Description

` SEM/EDS analysis of a corroded hexmesh ligament

◦ Exposed side – oxidation
◦ Creviced region – carburization
◦ Underside – carburization & sulfidation/oxidation

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 Hexmesh Failure Description

` Hexmesh has experienced only moderate oxidation on the freely flowing

flue gas side
` Hexmesh has experienced severe oxidation, carburization, and
sulfidation in confined spaces (i.e. where flue gas circulation was limited
and catalyst/coke fines could accumulate)
` Estimated corrosion penetration rate is on the order of 2 to 20 mpy (0.05
to 0.5 mm)
` Carbon (coke fines) was detected in significant concentrations in
surface scale along with sulfides
` Some of the oxide/sulfide species identified in the scales by
SEM/EDS/XRD are:
◦ CrO FeO Cr-Fe-O
◦ Cr-S FeS Cr-S-O-Fe
◦ NiSx

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 Hexmesh Failure Model

` Simulated hot corrosion of stainless steel in flue gas with residual

oxygen, sulfur species, and carbonaceous matter
◦ Typical flue gas (mol%): CO 0.05; SO2 0.13; O2 1.00; H2O 7.10; CO2 15.43;
and N2 76.29
` Relate metal oxides and sulfides in hexmesh scale to elevated
temperature thermochemical stability diagram of Fe-Cr-Ni/S-O2 system
` Model hot corrosion of hexmesh grid using ASSET program that was
developed under a MTI contract for a consortium of petrochemical
companies
◦ Nominal flue gas composition
◦ A representative cyclone temperature – 1400oF (760oC)
◦ Simulate depletion of oxygen by Fe-Cr-Ni and/or carbon in confined spaces of
hexmesh
◦ Simulate accumulation of coke fines in the confined spaces of hexmesh
` Estimate hot corrosion using ASSET program

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 Hexmesh Failure Model
Theoretical Background
` Thermochemical Stability Diagram delineates domains of stable
metal, metal oxides, & metal sulfides
Fe-Cr-Ni/S-O2 System at 1292°F (700°C)

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 Hexmesh Failure Model
Results
` Input: Type 304 SS exposed to FCC regenerator flue gas undergoing
oxygen depletion with or without carbon at 1400oF (760oC)
` Result: Increasing reducing environment promotes sulfidizing condition
(↑ H2S), higher sulfide/oxide ratio, and higher metal penetration rate
Flue Gas Input Calculated Values

Carbon Oxygen pp(H2S) Metal Sulfides Metal Oxides Penetration Rate

mol % mol % psia mol % mol % mm/y (mpy)

Oxygen-rich Environment
0 1 <1.0E-13 0 98 0
0 0.1 <1.0E-09 0 98 0
0 0.01 8.1E-06 4 93 0.07 (2.7)
0 0.001 2.8E-05 6 91 0.09 (3.6)
Carbon-rich Environment
1 1 2.8E-05 6 91 0.09 (3.6)
1.1 1 6.2E-04 28 69 0.19 (7.5)
4 1 2.4E-03 85 14 0.38 (15)
10 1 2.2E-03 85 13 0.48 (19)

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 Hexmesh Failure Model
Results

` Carburization of Type 304 SS in the presence of carbon

(coke fines) is predicted by ASSET at temperatures of
1200oF to 1400oF (649oC to 760oC)
` Carburization rate increases with an increase in
temperature
◦ Calculated Rate: 4 mpy (0.1 mm/y) at 1200oF and 5 mpy (0.12 mm/y)
at 1400oF
` Calculated carburization rates are on the same order as that
observed in the hexmesh grid

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 Hexmesh Failure Model
Results

` Coke fines collected in the confined spaces of the refractory

lining, i.e. ceramic/grid crevices and gaps between the cyclone
walls, produced a local reducing environment that promoted
sulfidation/oxidation of the hexmesh grid and the cyclone metal
(i.e. Type 304 stainless steel) at the operating temperatures
` Coke fines also promoted carburization of the metal in the
confined places where they collected
` Flue gas inside the cyclone is moderately oxidizing because of
the residual oxygen and, thus, not overtly corrosive to the freely
exposed hexmesh grid and the wall plate
` Hot corrosion, i.e. sulfidation/oxidation and carburization, of Type
304 stainless steel and a few candidate alloys for the
hexmesh/wall plate was successfully modeled with the ASSET
program from MTI
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 Hexmesh Failure Model
Results

` One or more of the following measures could be used to

remedy hot corrosion, i.e. sulfidation/oxidation and
carburization of the hexmesh and cyclone walls
` Minimize coke fine entry into the cyclone
◦ More efficient decoking of flue gas in the regenerators by improved
regenerator design to minimize coke on catalyst and after burn
◦ Minimize gaps between refractory and cyclone body
` Use a more corrosion resistant alloy compared to Type 304
stainless steel
◦ A few candidate alloys are: Type 310, Type 316, and Type 347
` Lower sulfidation potential of the flue gas with less sulfur in
the FCC feed

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 Remaining Cyclone Life

` Evaluation
◦ Cost of replacement vs. repair
◦ Evaluation of material sampling from previous
turnarounds
x Weldability
x Toughness
x Creep

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 Inspection

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 Inspection

` Metallic:
◦ Visual
◦ Penetrant
◦ Material sampling
` Refractory:
◦ Visual

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 Inspection
Metallic

` Visual:
◦ External erosion
◦ Hangers and all structural welds
◦ Look for sharp notches, cracks, or erosion of hangers
◦ Crossover duct
◦ Dipleg attachments
◦ Dipleg and cyclone bracing
◦ Trickle valve wear

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 Inspection
Metallic

` Penetrant:
◦ Hangers and all structural welds
◦ Crossover duct
◦ Dipleg attachments
◦ Weld repairs

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 Inspection
Metallic

` Material Sampling: (In-situ metallography or sample)

◦ Any areas found to be cracked, eroded
◦ Sample of refractory anchor material, weld and base
metal in refractory repair area
◦ Representative samples for metallurgical assessment to
assess degradation rates

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 Inspection
Refractory

` Visual:
◦ Erosion
◦ Spalling
◦ Bulging of lining, loss of attachment weld
x Corrosion
x Poor attachment weld

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 Cyclone Design Operation and Monitoring
• Best Practice Design Guidelines • Process Monitoring
Developed From: • Erosion Rate Prediction Tool
• Past experience
• Design & Engineering Companies
• Cyclone Vendors
• PSRI
• Other industry sources

Inspections and
Maintenance
Lessons Learned Improvements • Planned and Expected
• No Surprises

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 Mike Maholland Doug McAulay
FCC Process Specialist Principal Mechanical Engineer
Chevron Global Manufacturing BP Refining Technology

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