Materials Selection

for
Processing Equipment

Don Bagnoli
 Selection criteria We will cover

• Corrosion resistance
• Mechanical properties • Mechanical properties
• Stability of properties • Stability of properties
• Fabricability • Refinery Applications
• Availability
• Cost
 Characterize all process streams
Are any streams?
• Corrosive – if so, in what forms
• Erosive
• Likely to cause fouling

Can potentially harmful products form or

changes in temperature develop?
• Under normal conditions
• During upsets

What are risk and consequence of a leak

(risk based inspection / API 580)?
• Fire / explosion
• Health hazards
• Pollution
Define all process conditions during
Startup
Operation
Upset
Shutdown

• Pressures
• Temperatures
• Flow rates
• Frequency and amplitude of any cycles due to:
– Pressure
– Temperature
– Mechanical conditions
 Important items to focus upon
when selecting materials
• High temperature hydrogen
• Cryogenic temperatures
• Equipment with temperatures > 1000oF (540oC)
• Acids
• Unusual chemicals (BF3, sulfolane etc)
• Dewpoint corrosives (CO2, Cl2 etc)
• Quality of cooling water
• Is the catalyst regenerated in situ?
• Do heat exchangers have more than one shell in series?
The ASME pressure vessel code covers:
• Acceptable materials and allowable stresses
• Calculation of minimum thickness based
upon design temperature / pressure
• Provision of corrosion allowance
• Welding procedure and PWHT

The code does not cover:

• Effect of process environment:
– Corrosion
– Effect on mechanical properties
Extract from ASME
pressure vessel
code showing effect
of temperature on
allowable stresses

Above 1100oF carbon

steel and low alloy
steels experience a
significant decrease
in allowable stress.
Here stainless steels
are required.
ASME pressure vessel code is based on secondary creep
Furnace tubes are based on time-to-fracture
Illustration of tensile testing machine

Load cell

Specimen

Moving
crosshead
Brittle failure Ductile failure
Example of brittle failure

Ammonia converter during hydrotest

Charpy test
for impact
toughness
Charpy impact test machine
Ductile to brittle transition curve
Impact energy ft-lbs

Temperature oC
 Different
steel grades

Extract from
post-1987
ASME
These are
pressure limiting curves
vessel code Before 1987
showing there were no
toughness limiting curves
requirements above -20oF
This curve shows
the use of Ni to
lower the
ductile-to-brittle
transition
temperature
 Stability of properties

• Sensitization
– Intergranular corrosion of austenitics
• Embrittlement
– Sigma or other embrittling phases in
some austenitics
– 475oC (885oF) embrittlement of ferritics
and martensitics
• Toughness transition
– Annealed austenitics are immune
Example of
sigma phase
formation in
Type 347
stainless steel
overlay on
Cr-Mo steel
nozzle flange Crack
surface ring
groove
Cross
section of
the ring
groove
The Type 347
was
sigmatized
during PWHT
of the Cr-Mo
steel
 Effect of time and temperature on
475oC (885oF) embrittlement of
Type 446 (27Cr)

eg. distillation tower trays can become brittle and fail

 Refining processes

• Desalting • Hydrocracking
• Atmospheric distillation • Hydrogen plant
• Vacuum distillation • Gas plant (light ends)
• Catalytic cracking • Gas treating (amine)
• Delayed coking • Sour water treatment
• Hydrofinishing • Alkylation
• Hydrodesulfurizion • Isomerization
• Catalytic reforming
Typical petroleum refinery process diagram
with common associated corrodents
Crude distillation
 Average corrosion rates
High temperature sulfur corrosion
Hydrogen free environment
Corrosion of steels in crude oil containing
naphthenic acid and sulfur compounds
Corrosion of steels in crude oil containing
naphthenic acid and sulfur compounds
 Crude distillation

• Type 316 stainless steel is used for heater tubes

and transfer lines if naphthenic acid is present
• For very aggressive naphthenic acid service
Type 317 is used in high velocity areas
• For high sulfur crudes without naphthenic acid,
Type 304 stainless steel is often required for
heater tubes and transfer lines
Fluid catalytic cracking
Fluid catalytic cracking (FCC)
regenerator corrosion

This dark
deposit is the
imprint of the
NiS corrosion
product on
hexmesh which
was in contact
with the weld.
NiS formed by
sulfidation of
the high nickel
welding
consumable
(Inco Weld A)
Hydrodesulfurizers and Hydrofiners
 Cr-Mo heat exchanger which failed after only a couple of
months in H2 – H2S service

Problems: tube failure + blockage of the reactor due to

corrosion products
This is the previous diagram for sulfidation resistance showing
the beneficial effects of Cr
Not applicable for H2 – H2S as seen in the next figure
 Corrosion rate curves for H2 – H2S environments

H2 destroys the
protective sulfide
scale which forms
and an 18-8 type
of stainless steel
is required
 Hydrodesulfurizer service

• Type 410 stainless steel and Cr-Mo steels are

not resistant to H2 – H2S service at high
temperatures (over 288oC / 550oF)
• Types 304 and 347 stainless steel are required
for H2 – H2S service at high temperatures
(over 288oC / 550oF)
• Stabilized stainless steels, Types 347 and 321,
are required at many low temperature
locations to resist polythionic acid stress
corrosion cracking (PSCC)
• Need to consider hydrogen attack for carbon
steel and low alloy steels
Hydrogen plant
Radiographs showing two levels of creep damage

Tube where heaviest creep damage was experienced

Tube where intermediate damage was experienced

 Hydrogen plant

• Sulfur is removed for this process

• Steam methane reformer tubes use HP-Mod
alloy (25Cr – 35Ni + additions)
• At low temperatures carbonic acid is formed
and Type 304L is used instead of carbon steel
Delayed coking
Coker heater tubes

9Cr-1Mo tube failed due to carburization and creep

Use LCC to compare 9Cr-1Mo versus Type 347
 Delayed coking

• Type 347 stainless steel is used for heater tubes

in high severity service instead of 9Cr-1Mo
• Coke drums:
– Type 410 stainless steel cladding is used
– If naphthenic acid is present Type 316
stainless steel is used
Ethylene (olefins) unit
Process layout – typical ethylene heater
Bulging of ethylene heater tube due to carburization
Creep cracks in the carburized region of tube wall
Cross section of
carburized tube showing
carburization initiation
sites at casting defects
 Damage Mechanisms in
Multiwall Ammonia Converters
• Hydrogen related attack (surface flaws) or embrittlement
(sub-surface flaws), with the later occurring due to
diffusion of atomic hydrogen into the steel.
• Potential growth of minor construction flaws due to
operational cycling (temperatures and pressures).
• Potential growth of minor construction flaws due to
operational cycling (temperatures and pressures).
• Embrittlement and subsequent cracking of Type 347
stainless steel overlay or cladding, in the event that it has
been used.
• Nitriding of the inner layer of the vessel with a related
increase in hardness
Head-to-shell joint for hot hydrogen service
 Thank You
for
Your Interest