Potential Damage Mechanism in Fertilizer Plant

1. Lessons Learnt from Risk-Based Assessments on Eight Ammonia Plants

and Downstream Urea, Nitric Acid and Fertilizer Plants
The following asset types were most at risk of suffering a failure event.
 Primary reformer outlet manifolds – creep fatigue from system generated bending loads and
use of Inconel 182 weld metal.
 Primary reformer effluent duct coils – end of creep life / localised hot areas.
 Reformed gas waste heat boilers – Crevice corrosion (tube to tube sheet).
 Reformed gas waste heat boilers – Long term / short term overheating leading to tube failures
from hydrogen damage, creep and tensile overload.
 C 0.5Mo steel manufactured vessels and piping systems in pre 1980 plants – HTHA from
operation above CS Nelson Curve.
 C 0.5Mo steel manufactured vessels in pre 1970 plants – H2 Assisted Cracking of excessively
hard welds (PWHT soak temperature too low).
 Synloop alloy steel (P22 CrMo) vessels/exchangers in hydrogen service – Cracking of incorrectly
post weld heat treated welds.
 Ammonia converters – H2 assisted thermal fatigue cracking (material properties, poor welding,
cyclic operation and start-up procedure).
 Low-temperature vessels in back end of plant – risk of brittle fracture in the event of a low-
temperature excursion followed by sudden repressure.
 Stainless steel vessels and exchangers – Chloride-induced stress corrosion cracking; external
surface (under lagging) and internal surface (chloride levels concentrate over many years
service).
 Carbon steel equipment in CO2 removal section (KO Pots, stripper, absorber) where there is a
risk of ‘wet CO2’ pitting attack.
 Cooling water heat exchangers – tube failures resulting from poorly managed water treatment
program or excessively low water velocities (Under-deposit corrosion, micro- bially-induced
corrosion).
 Cracking of non-annealed Inconel 600 expansion bellows and exchanger tubes in hydrogen
service.

It is considered that a risk based approach to assessment of plant has resulted in the avoidance of a
significant number of possible failures which had the potential to cause significant loss of life,
damage to plant or both. A listing of many of these is included in Table 1 -1.
Table 1-1 Summary of Problems Found on Eight Ammonia and Downstream Plants Through a Risk- Based Assessment Analysis
Process
Plant Age (y) Equipment type Damage mechanism highlighted On-stream failure prevented
type
A1 Ammonia 35 Reformer outlet Leaking reformed gas to atmosphere,
Creep fatigue cracking – bend- ing
manifold tee- risk
moments in manifold arms
cone of fire & personnel injury; 2-3
weeks lost production
 Process
Plant Age (y) Equipment type Damage mechanism highlighted On-stream failure prevented
type
Mixed feed coil Potential for equipment
(reformer Creep - localised damage due to coil
damage, 2-3 weeks lost
effluent) design (hot spots)
production
Potential for tube failures, 1-2
Hydrogen damage / creep – long
Reformed gas weeks to plug failed tubes / 6
term localised overheating of
WHB weeks to re-tube
tubes
boiler
Leaking process gas to atmosphere,
H2-assisted cracking – PWHT soak
HT shift risk
temperature too low, HAZ
converter of fire & personnel injury; 2-3
too hard
weeks lost production
Leaking process gas to atmosphere,
Stress corrosion cracking of
Mixed-feed risk
expansion bellows – low level
preheater of fire & personnel injury; 2-3
chlorides in steam
weeks lost production
Tube failure; 2-3 days to plug failed
Microbial induced corrosion –
Sulfinol cooler tubes / 6 weeks to re-tube
cooling water velocities too low
exchanger.
Leaking process gas to atmosphere,
H2-assisted cracking – PWHT soak
risk
temperature too low, HAZ
Methanator of fire & personnel injury; 2-3
too hard
weeks lost production
Leaking process gas to atmosphere,
H2-assisted thermal fatigue
Ammonia risk
cracking – S/up procedure &
converters of fire, explosion & personnel
material properties
injury; >3 weeks lost production
Localised corrosion of liner –
operational problems with purge Corrosion damage to shell; plant
Urea reactor off line for 2-3 weeks to repair.
water
Potential for catastrophic failure of
Potential for brittle fracture
Ammonia pressure vessel, severe property
A2 Urea 35 during low temperature/re-
collector damage, high personnel safety &
pressure excursion
environment risk.
Localised corrosion adjacent
baffles – stainless steel baffles, Perforation of shell; cooler off line
MEA coolers for 1-2 days to repair.
steel shell
B1 Ammonia 35 Potential for equipment
HT S/H steam coil Carbon steel sections - end of
damage, 2-3 weeks lost
- reformer creep life, CrMo sections - OK
production
Leaking reformed gas to
Reformer outlet Localised creep fatigue damage atmosphere, risk of fire & personnel
manifold due to manifold design. injury; 2-3 weeks lost production
Potential for tube failures, 1-2 weeks
Hydrogen damage / creep – long
Reformed gas to
term localised overheating of
WHB plug failed tubes / 6 weeks to
tubes
re-tube boiler
Potential for catastrophic failure of
Potential for brittle fracture
Purge gas pressure vessel, severe property
during low temperature/re-
separator damage, high personnel safety &
pressure excursion
environment risk.
Creep - localised damage due to coil Potential for equipment
Auxiliary boiler
design (hot spots) damage, 2-3 weeks lost
 Process
Plant Age (y) Equipment type Damage mechanism highlighted On-stream failure prevented
type
production
Potential for catastrophic failure of
HTHA of C 0.5Mo steel
pressure vessel, severe property
operating above CS Nelson
Methanator damage, high personnel safety &
Curve.
environment risk.
Potential for catastrophic failure of
HTHA of C 0.5Mo steel
NH3 converter pressure vessel, severe property
operating above CS Nelson
effluent exch. damage, high personnel safety &
Curve.
environment risk.
Potential for catastrophic failure of
HTHA of C 0.5Mo steel pressure system, severe property
NH3 converter operating above CS Nelson damage,
Effluent piping Curve. high personnel safety & environment
risk.
Leaking process gas to atmosphere,
Chloride induced stress
CO2 stripper risk
corrosion cracking beneath
gas reboiler of fire & personnel injury; 2-3
lagging
weeks lost production
Leaking process gas to
Chloride induced stress
Shift effluent atmosphere, risk of fire &
corrosion cracking beneath
BFW heater personnel injury; 2-3 weeks lost
lagging
production
Potential for catastrophic failure of
Transition section Potential for HTHA damage due to pressure system, severe property
– Sec. reformer on-going refractory problems damage, high personnel safety &
environment risk.
Thermal fatigue cracking due to Leaking HP steam to atmosphere; >3
fast start-up procedure (heavy weeks lost production,
Steam drum
wall drum) potential for personnel injury
Localised corrosion from poor
cooling water treatment (scaling Tube failure; 2-3 days to plug failed
Cooler
leading to high tube wall tubes / 10 weeks to re-tube
condenser
B2 Nitric acid 35 temperatures). exchanger.
Tubes at end of life due to
Waste heat prolonged operation 450 Tube failure; 2-3 days to plug failed
boiler embrittlement range. tubes / 6 weeks to re-tube boiler.
Leaking reformed gas to
Reformer outlet Localised creep fatigue damage atmosphere, risk of fire & personnel
manifold due to manifold sag. injury; 2-3 weeks lost
production
Leaking reformed gas to
Primary to sec Localised creep fatigue damage of atmosphere, risk of fire & personnel
C Ammonia 30 reformer pipe Inconel 182 welds injury; 2-3 weeks lost production
Reformed gas Localised corrosion of tubes in Tube failure; 1 week to plug failed
WHB tube to tubesheet crevice tubes / 4 weeks to re-tube boiler.
Potential for tube failures, 1-2
Hydrogen damage / creep – long
Reformed gas weeks to plug failed tubes / 6
term localised overheating of
WHB weeks to re-tube
tubes
boiler
 Process
Plant Age (y) Equipment type Damage mechanism highlighted On-stream failure prevented
type
Potential for catastrophic failure of
HTHA of C 0.5Mo steel
pressure vessel, severe property
operating above CS Nelson
HT shift damage, high personnel safety &
Curve.
environment risk.
Reformed gas Localised corrosion of tubes in Tube failure; 1 week to plug failed
WHB tube to tubesheet crevice tubes / 4 weeks to re-tube boiler.
Potential for tube failures, 1-2
Reformed gas Hydrogen damage / creep – long
weeks to plug failed tubes / 6
WHB term localised overheating of tubes
weeks to re-tube boiler
D Ammonia 35 Potential for equipment
Sec process
Coils approaching end of creep life damage, 2-3 weeks lost
steam S/H
production
Perforation of shell, process gas
Localised pitting from carbonic acid
to atmosphere; 1 week lost
attack in high impingement
Knock-out pot production to
areas
repair, potential fire risk
Potential for catastrophic failure of
HTHA of C 0.5Mo steel
pressure system, severe property
operating above CS Nelson
Synloop piping damage, high personnel safety &
Curve.
environment risk.
Leaking reformed gas to atmosphere,
Reformer outlet Localised creep fatigue damage risk
manifold due to manifold sag. of fire & personnel injury; 2-3 weeks
lost production
E Ammonia 20
Leaking reformed gas to atmosphere,
Ref product / feed Hydrogen embrittlement of risk
gas exch Inconel 600 bellows. of fire & personnel injury; 2-3
weeks lost production
Leaking reformed gas to
Hydrogen assisted cracking of
Syn Loop BFW atmosphere, risk of fire & personnel
channel to tubesheet weld
Pre-heater injury; 2-3 weeks lost
(PWHT inadequate)
F Ammonia 2 production
Risk of tube to tubesheet weld Tube failure; 2 weeks to repair/plug
cracking – weld procedure cracked welds / 6 weeks to re-tube
Synloop WHB
inadequate boiler.
Potential for tube failures, 1-2 weeks
Hydrogen damage / creep – long
Reformed gas to
term localised overheating of
WHB plug failed tubes / 6 weeks to
tubes
re-tube boiler
Burner failure; plant off line for 1-2
Sec reformer Creep fatigue cracking at
weeks to repair existing / install
Burner dissimilar metal weld
new burner
Potential for catastrophic failure of
Potential for brittle fracture
Purge gas pressure vessel, severe property
during low temperature/re-
separator damage, high personnel safety &
pressure excursion
environment risk.
Cracking of non annealed
Steam pre Inconel 600 exchanger tube Tube failure; 2 weeks to plug failed
super-heater return bends tubes / 6 weeks to re-tube boiler.
 Process
Plant Age (y) Equipment type Damage mechanism highlighted On-stream failure prevented
type
SCC of tube to tubesheet welds Tube failure; 2 weeks to repair/plug
MP reformed gas – caustic wash during cracked welds / 6 weeks to re-tube
cooler commission boiler.
Potential for tube failures, 1-2
Reformed gas Hydrogen damage / creep – long
weeks to plug failed tubes / 6
WHB term localised overheating of tubes
weeks to re-tube boiler
G Ammonia 2 Leaking reformed gas to atmosphere,
Creep fatigue cracking of outlet risk
Reformer manifold tee to cone weld of fire & personnel injury; 2-3
weeks lost production
Potential for catastrophic failure of
Potential for brittle fracture
pressure vessel, severe property
during low temperature/re-
MP flash drum damage, high personnel safety &
pressure excursion
environment risk.
Leaking reformed gas to
Creep fatigue cracking of outlet atmosphere, risk of fire & personnel
Reformer manifold tee to cone weld injury; 2-3 weeks lost
production
Potential for tube failures, 1-2 weeks
Hydrogen damage / creep – long
Reformed gas to
term localised overheating of
WHB plug failed tubes / 6 weeks to
tubes
re-tube boiler
Leaking reformed gas to atmosphere,
H2-assisted cracking of inlet
H1 Ammonia 2 Reformed gas risk
nozzle to channel weld;
WHB of fire & personnel injury; 2-3
inadequate PWHT
weeks lost production
Tube failure; 2-3 days to plug failed
Synloop Microbial Induced Corrosion –
tubes / 4 weeks to re-tube
intercoolers cooling water velocities too low
exchanger.
Potential for catastrophic failure of
Potential for brittle fracture
pressure vessel, severe property
during low temperature/re-
MP flash drum damage, high personnel safety &
pressure excursion
environment risk.
Cooler SCC of stainless steel inlet
condenser nozzle in cooling water jacket Plant off line for 5-7 days to repair.
H2 Nitric acid 2 Potential for localised pitting Tube failure; 2-3 days to plug failed
corrosion -condensing droplets of tubes / 6 weeks to re-tube
Economiser
nitric acid exchanger.
Ammoni
Pipe reactor Localised corrosion (3mm/yr); Plant off line for 1-2 days,
H3 um 2
separator material inadequate for duty potential for personnel injury.
nitrate

2. DAMAGE MECHANISMS RELATED TO AMMONIA and UREA

PLANTS
Some of the most common damage mechanisms in the Ammonia/Urea plant, refining and chemical
processing industries are:
  Wet H2S Damage, which can occur when atomic hydrogen from wet H2S corrosion reactions
enters and weakens the steel.
 CO2 Corrosion, which is a form of degradation that occurs when dissolved CO2 in condensate
forms carbonic acid, which corrodes steels.
 Corrosion Under Insulation (CUI), which occurs when moisture builds up on the surface of
insulated equipment.
 Hydrogen Embrittlement, which happens when atomic hydrogen infuses into certain higher
strength steels and causes them to become brittle.
 Brittle Fracture, which is the sudden, very rapid fracture under stress where the material
exhibits little or no evidence of ductility or plastic degradation before the fracture occurs.
 High Temperature Hydrogen Attack (HTHA), a mechanism that can affect equipment that is
exposed to hydrogen at elevated temperatures (at least 400 °F or 204 °C).
 Sulfidation Corrosion, a type of corrosion that occurs at temperatures above 500 °F (260 °C) due
to sulfur compounds in crude.

3. Tips on Establishing an Inspection Strategy for a Fertilizer Plant

Three metallurgical damage mechanisms commonly affect ammonia equipment and are discussed in
relation to process variables, process equipment and materials of construction:

 High-temperature hydrogen attack (HTHA)

Susceptible materials include high-strength, low-alloy steels (legacy C–½Mo steels), plain carbon
steels, non-post-weld heat-treated (PWHT) welds, and copper alloys.
Typical concerns on the shift unit and equipment throughout the ammonia process, including
equipment in the shift units (both high and low shift), methanation and synthesis loop, where
temperatures are above 204°C (400°F). However, may be present in secondary unit pressure
shells due to refractory failure.
Synthesis loop equipment, particularly converters without furnace stress relief or operating at
high temperatures on the pressure shells, and startup heater coils are also vulnerable points for
attack. Additionally, hot spots from refractory failures can occur in the primary reformer outlet,
in secondary reformer and waste heat boilers, molsieves and pressure envelopes
 Environmentally assisted stress corrosion cracking (SCC)
The most common cracking mechanism detected in ammonia storage tanks, spheres and other
process equipment.
Susceptible materials to NH3 SCC include carbon steel, low-alloy steels and stainless steels
exposed to high O2 levels or chlorides. Chlorides may be present in insulation or cooling waters,
both of which can result in SCC of stainless steels.
Affected NH3 process units include susceptible materials in the convection unit, such as headers
exposed to chlorides in insulation; primary reformer inlet pigtails; the synthetic loop startup
heater coils, which may be exposed to atmospheric SCC promoters; and exchangers with
seawater or cooling water with high chloride content.
High hardness material is more susceptible, with the heat-affected zone (HAZ) and areas with
localized stress being the most vulnerable.
 Brittle fracture
NH3 process units where brittle fracture is a concern include the synthesis loop, syngas
compression, refrigeration, molsieves, NH3 wash and cryogenic purification. Equipment such as
chillers, flash drums and NH3 product separators may be susceptible to reaching temperatures
below the ductile brittle transition temperature (DBTT) for steels. Depressurization will lower
temperatures.
Carbon steels and low-alloy steels with low toughness and an existing flaw or crack, and
materials that contain residual stresses due to improper stress relief or that do not undergo
PWHT, are more susceptible. Normalized steel is less susceptible to brittle fracture than steels
having undergone other treatment.