Experiences with 2.
25Cr-1Mo-Steel
Equipment in the Ammonia Synthesis
Loop after 30 Years in Service
After 30 years in service, the synthesis loop of the BASF Ammonia IV plant underwent intensive
inspection activities during the turnaround in the year 2013. Initial damages in the ammonia
converters caused by hydrogen induced cracking were experienced in the year 1990 after only 8 years
in service which finally led to the replacement of the converter in 1996. Since the operating
conditions cannot be modified, the only solutions were the reduction of stresses in the welds by an
optimization of the converter design and monitoring of possible crack growth by means of NDT.
Based on these experiences, the inspection and fitness-for-service evaluation was focused mainly on
the converters. In 2007, the waste heat boiler showed comparable damage which indicated that the
remaining equipment in the synthesis loop may also be affected. Prior to the turnaround in 2013, the
inspection scope was enhanced as a result of a risk assessment evaluation. The outcome of the
inspection activities is summarized in the paper.
Bernhard Geis
BASF SE
Hans-Jürgen Bassler
BASF SE
Introduction
D uring a turnaround of the Ammonia
Plant IV at Ludwigshafen in the year
2013, the synthesis loop section (Figure
1, Table 1) using the C.F. Braun process with hot
known at that time [1]. The cracking was induced
by the now well-known combination of nitriding
and high temperature hydrogen attack (HTHA)
in ammonia containing synthesis gas at high
wall converters underwent an intensive inspec- temperatures leading to cracking in the girth
tion for damage caused by high temperature hy- welds of the converter driven by high stresses in
drogen attack. Retrospectively, the damage in the that area. The most important finding was that
closing weld seam of converter C702 was first the Nelson diagram may lead to misleading re-
noticed in 1990 after only 8 years in service. sults under the specific condition in ammonia
Many efforts were made to identify the root containing synthesis gas (Figure 2).
cause of the cracking which was completely un-
2014 11 AMMONIA TECHNICAL MANUAL
Figure 2: Operating limits of low alloyed steels
in hydrogen service to avoid decarburization and
Figure 1: Process scheme and operation condi- fissuring
tions of synthesis loop, Ammonia IV plant
Meanwhile, the first converter in series, C701,
The evaluation of the damage mechanism and was also inspected intensively. Some minor
development of the repair program for the dam- cracks were found which were removed in the
aged converter was a considerable effort [2]. The field without weld repair.
entire converter had to be moved to the fabrica-
tor’s shop. The 145 mm thick cracked weld seam Knowing the damage mechanism, it was antici-
had to be completely removed and re-welded fol- pated that new cracking and crack extension may
lowed by an optimized local post-weld heat occur. To prevent a new leakage during further
treatment. operation, an inspection concept was evaluated
using a specifically developed NDT concept (see
below) which was applied to all circumferential
welds of both converters and the connecting
welds to the heat exchangers. The testing interval
was limited to a maximum of 2.5 years to ensure
that the possible cracks can be identified in an
early state.
During the first periodic inspection in 1992, first
crack indications were observed by ultrasonic
testing (depth: approx. 2.5 mm, but certainly < 3
mm disc shape reflector (DSR) + 2dB) again in
10% of the circumference of the closing weld
seam of the converter C702 after 28 months in
service. The crack depth could not be determined
exactly indicating that the crack size was far be-
low the critical one.
Table 1: Design and materials data of main
components in the synthesis loop
To assure the integrity of the converter for fur-
ther operation a phenomenological crack propa-
gation model was designed since a physically
verified cracking mechanism model was not
available for this type of failure. This model was
required to determine convenient NDT-
inspection intervals and to judge on the convert-
ers remaining lifetime.
AMMONIA TECHNICAL MANUAL 12 2014
The crack propagation in the converters is basi- The additional application of fracture mechanics
cally a function of stress level (residual and op- gave the possibility to evaluate the critical depth
eration stresses), operation conditions (tempera- for a circumferential crack on basis of accurate
ture, pressure, ammonia concentration etc.) and knowledge on the material characteristic values
microstructural changes due to nitrogen diffusion and the stress distribution resulting from load and
into the lattice. The crack propagation model was residual stresses. For the final girth seam of con-
realized by evaluating worst-case assumptions verter C702 a minimum allowable crack depth of
from manufacturing details (i.e. the interaction of 45 mm was calculated (dotted line in Figure 3).
PWHT parameters and residual stresses) and the
runtimes of different converters between NDT Based on this model it was decided to operate the
crack depth measurements. Beside the evaluating converter further with shortened inspection inter-
results of both BASF converters also the results vals to monitor the crack propagation safely be-
of the similarly damaged converters of Grand fore it became critical. During the next inspec-
Paroisse, France, were taken into account [3]. tion 15 months later, 4 mm deep cracking was
measured along 40% of the circumference. This
Figure 3 shows the model in a time vs. crack result was still uncritical but it became clear that
depth diagram. The hypothetical crack propaga- the crack propagation follows not a linear time
tion area (grey field) is limited by boundary law but more an accelerating exponential one.
curve approximations representing the best case This finding led to the decision in the year 1994
assumption (green line) and the worst case ap- to replace the converter as soon as possible. To
proximation (red line). Further NDT investiga- assure safe operation of the cracked converter,
tions (blue line) until removing the converter the crack propagation was monitored intensively
from operation confirmed that the predicted every 12 months of operation. Consequently, it
crack propagation rate was conservative and un- was stated in February 1995 that taking the worst
critical. case approximation of the crack propagation
model into account, the converter can only be
operated safely until September 1996.
New converter design
The first C702 converter was designed according
to German AD pressure vessel code. Therefore,
the required minimum wall thickness was signif-
icantly lower compared to ASME design. As a
consequence of a thinner wall, the stress level in
the AD design converter was higher (Figure 4).
The decisive role of the mechanical stresses be-
came obvious since other converters built ac-
cording to ASME design show no or minor prob-
lems while converters built according to AD or
Figure 3: Measured and conservatively approx- the French CODAP pressure vessel code failed.
imated crack propagation [3]
2014 13 AMMONIA TECHNICAL MANUAL
In 1989 a leak was discovered in one of the three sidual and operation stresses). This was accom-
Braun type converters at Grand Paroisse (G.P.), plished by the following:
France, after only 4 years in operation [3-5].
Cracks were also detected in the other two. The reducing the design stress level by about
damage mechanism was comparable to the 15-20% (additional safety factor: 0.85)
BASF converters. The G.P. converters were de- under maximum allowed AD code value
signed according CODAP. Compared to AD (red-to-green arrow in Figure 4),
code, CODAP allows a higher stress level and PWHT of the complete converter in a
consequently a lower minimum wall-thickness furnace instead of localized PWHT of the
(Table 2). All G.P. converters and the BASF welds in order to minimize residual
C702 were repaired by welding a complete new stresses,
final girth seam into the shell. But in conse- Transferring the closing weld and skirt
quence new cracks were formed in two of the support away from the circumferential
G.P. converters and also in BASF C702. weld at the lower spherical head to pre-
vent additional bending stresses.
200
Max. allowable Design Stresses
190 at 430 °C according:
180 CODAP = 180 MPa
NDT inspection concept
Design Stress MPa
170 AD/VdTÜV = 169 MPa
(1st C702)
160
The cut-out of the damaged weld of the C702
150 ASME = 148 MPa
was used as calibration sample to evaluate ade-
140
130
ASME SA336‐F22
quate non-destructive testing (NDT) methods by
120
VdTÜV 12CrMo910: Rp0.2 / 1.5
VdTÜV 12CrMo910: 100.000h / 1.5
AD/VdTÜV/ Safety
Factor 0.85 = 145 MPa
comparing the NDT results with metallographic
110 VdTÜV 12CrMo910: Rp0.2 / 1.5 * 0.85
(2nd C702 )
investigations of the crack size in different seg-
100
VdTÜV 12CrMo910: 100.000h / 1.5 * 0.85
ments of the weld. The outcome of this investiga-
400 410 420 430
Design Temperature °C
440 450
tion shows that the mechanized UT pulse-echo P-
Scan technology (Figure 5a,b) is adequate for the
Figure 4: Comparison of design stresses accord- detection and length-sizing of initial cracking.
ing different pressure vessel codes for Braun- Mechanized TOFD technology [6] is used for the
type converters verification of prominent P-Scan indications. For
the accurate measurement of the crack depth, two
Based on the finding that crack propagation different manual UT pulse-echo-technologies are
through the wall is driven by the stress level, the complementally applied using a customized
new converter design was optimized in a way to LLT-Probe and OMNISCAN phased array tech-
reduce the entire stress level to a minimum (re- nology (Figure 5c,d).
Table 2: Design data and operating conditions of Grand Paroisse (G.P.) and BASF converters
(*: Material: 2.25Cr-1Mo steel for all converters; **: At final girth seam)
AMMONIA TECHNICAL MANUAL 14 2014
10 years. To verify these results, it was decided
to use the opportunity of a catalyst change for in-
ternal inspection during the turnaround 2013.
Damage history of other
components
During the intensive inspections after the leakage
of the converter C702 in 1990, first crack indica-
tions were also found in the second converter
C701 having a lower ammonia content with a
depth of 4 mm. The crack propagation was moni-
Figure 5: NDT-inspection using mechanized P- tored in the same way as for converter C702. The
Scan (a,b) and phased array technique (c,d) on C701 had also been replaced in the year 2000 us-
the converter C702 ing the optimized design concept. Up to 2013, af-
ter 13 years in service, no NDT indications had
This combination of different technologies gave been observed.
the best accuracy for the exact crack measure-
ments in the length and depth directions. The The process gas cooler, W721, and the piping in
mechanized NDT technologies further assured a the synthesis loop were in service for 30 years
repetitious screening with sufficient accuracy since the start-up of the plant without any indica-
over the inspection intervals to ensure reliable tions or known damages before turnaround 2013.
monitoring of crack propagation. Internal visual and NDT inspection were there-
fore implemented in the scope of the turnaround
After baseline inspection and start-up of the new 2013.
converter in September 1996, this UT-inspection
concept has been applied on a regular basis (in- The waste heat boiler, W722, had to be replaced
spection interval: 2.5 years) in order to assure twice in the years 1987 and 1995 because of dif-
safe operation of the new converter, C702. Dur- ferent damage mechanisms such as ligament
ing the following two NDT inspections, no indi- cracks in the tube sheet, tube leakages caused by
cations for a crack formation were found. How- loosened ferrules which rotated in the gas flow
ever, in 2007 after being in service for 11 years, leading finally to abrasion damage of the tube
the first small indications (depth: approx. 1 mm, wall [7,8], and corrosion on the feed water side
but certainly < DSR 2 mm) in a weld were ob- caused by insufficient blow down. During shut-
served, although not in the closing weld seam. down in 2007, hydrogen induced cracking was
The depth of the indications was not precisely found in the fusion line between the 2.25Cr-
measurable because of a relatively high noise 1Mo-Steel and a Ni-Base-Alloy buffer weld at a
signal from the inner wall. During the following diaphragm seal which could not be weld repaired
inspection, cracks were slightly increased (ap- in a proper manner (Figure 6). Therefore it was
prox. 1.5 mm, DSR 2.5 mm) remaining still far decided to replace the waste heat boiler during
below the critical one and still being acceptable turnaround 2013.
in accordance with the maximum allowed defect
size of AD code (DSR 3 mm). Manual UT-pulse-
echo control measurements confirmed that the
indications were of only minor depth not exceed-
ing 2 mm for sure. Therefore, the new converter
was considered safe to operate for about another
2014 15 AMMONIA TECHNICAL MANUAL
Figure 7: Crack indication at the fillet weld at a
weldolet for temperature measurement
Figure 6: Crack indication along a Ni-Base-
Alloy buffer weld in the waste heat boiler W722 As a consequence of these findings, the inspec-
tion of all weldolets and nozzles in the syngas-
In April 2013, only a few days before shut-down, loop-piping were also included in the inspection
a leakage occurred in the outlet syngas piping of scope for the turnaround. Later inspections
the waste heat boiler W722. The damage was showed that the piping material itself was not af-
found precisely at a fillet weld between a wel- fected by hydrogen cracking in this area.
dolet and a thermowell (Figure 7). The metallo-
graphic investigation showed that the leakage
was caused by hydrogen induced brittle inter- Recent findings during turnaround
granular fracture, not only in the weld but also in 2013
the heat affected zone (HAZ). No indications for
nitriding were found in the damaged area be- During shutdown, the catalyst was removed from
cause of the relatively low temperature (< both converters which offered the opportunity to
320°C) in this area. The hardness values in the perform internal inspections to evaluate the dam-
weld (up to 500 HV Hardness Vickers) and the age state and to verify the NDT results of the
HAZ (up to 400 HV) showed very high hardness previous inspections. In the converter C702, the
compared to the base material (up to 185 HV) weld with the NDT indications endured an inten-
suggesting that the PWHT during fabrication was sive inspection first by spot metallographic repli-
insufficient or neglected. The typical combina- ca investigations followed by 100% magnetic
tion of nitriding and HTHA damage found in the particle testing. In the microstructure, nitriding
other parts of the synthesis loop may not explain and hydrogen induced cracking was found run-
this damage. It was assumed that a hydrogen- ning approximately parallel to the shell (solid
assisted cracking in the hard and brittle zone of wall, thickness 158 mm) surface with a depth of
the weld could have accumulated over the life- less than 2 mm (Figure 8). The depth of the
time during cool downs. cracks was measured by grinding a watch glass
shape into the shell until the material was free of
indications.
Prior to magnetic particle inspection it was nec-
essary to grind the complete weld surface. After
grinding, no additional crack indications were
AMMONIA TECHNICAL MANUAL 16 2014
found. These results correspond reasonably well
with the NDT results of 2010.After the internal
inspection, the external NDT inspection was re-
peated in order to gain a new baseline for future
inspections.
Comparable results were found in the converter
C701. Cracking can be identified only in the base
material by microstructural replica investigations
without previous surface grinding. The crack
depth was less than 1 mm.
Figure 9: Crack indication in the diaphragm
seal buffer weld and shell of process gas cooler
W721
Figure 8: Crack indication in a weld of convert-
er C702 Figure 10: Diffusion zone with fissuring in the
crevice area of a weldolet / pipe connection and
Comparable damage as found in 2007 in the cracking in the fillet weld
waste heat boiler, W722, was also observed in
the process gas cooler, W721, on the outlet side In the piping between W721 and W722, nitriding
at a diaphragm seal. In this case, cracking was and hydrogen attack was found on the inner sur-
found not in the fusion line between the 2.25Cr-1 face of the pipe material and also on several wel-
Mo-Steel and the Ni-Base-Alloy buffer weld, but dolets for thermocouples or pressure gauges, es-
rather directly in the buffer weld. After com- pecially in the crevices between the weldolet and
pletely grinding away the buffer weld in the the inserted pipe (Figure 10). In contrast to the
cracked area, it became clear that the base mate- above mentioned damage on a weldolet in the
rial also had hydrogen induced cracking along outlet piping of W722 where extreme high hard-
the fusion zone which may be the result of a dis- ness in the weld and the HAZ caused by poor
bonding process. Therefore, this area had to be manufacturing was the root cause of the damage,
machined out completely and repair-welded. these components showed the typically combina-
tion of nitriding and HTHA. The hardness values
After the first repair attempt, new porous indica- in the base metal and the fillet weld outside the
tions caused by hydrogen outgassing in the buff- nitrided zones are low (180 HV).
er weld were found and the procedure had to be
repeated once more with extended soaking time At these connections the synthesis gas is able to
at a higher preheating temperature. Besides this enter the crevice between the pipe and weldolet.
finding, hydrogen attack in a nitrided zone with a In this area, both components showed a nitrogen
depth of approximately 1-2 mm was also ob- diffusion zone parallel to the crevice line with a
served on the inside shell in this area (Figure 9). thickness of approximately 3 mm. The analysis
of the diffusion zone showed remarkably high
2014 17 AMMONIA TECHNICAL MANUAL
contents of nitrogen (0.41 %) and hydrogen that a disbonding process along the fusion line
(251 ppm) and extremely high (> 600 HV) hard- between the 2.25Cr-1Mo-Steel tube and the Ni-
ness values. Fissuring was only found in these Base-Alloy weld was the root cause of this be-
brittle zones which appeared parallel to the sur- havior (Figure 13). Furthermore, it was remark-
face line. The bulk material in the weldolet and able that the Ni-Base-Alloy also showed a small
the pipe outside of the nitrogen diffusion zones nitrogen diffusion zone (nitrogen: 0.12 %; hy-
near the surfaces showed no damage indications. drogen: <10 ppm) to a depth of 40 µm along the
At the end of the crevice, a brittle crack was also fusion line with small cracks in it (Figure 14).
observed through the fillet weld which is driven These results are very surprising because no gas
by high stresses in this zone. leakage into the feed water had been experienced
during operation.
Internal inspection of the piping was only possi-
ble at the section point where the “old” W722 Besides these findings in the fusion line, fissur-
was removed from the plant. The metallographic ing in the tube material itself was also found
investigations also showed a nitrogen diffusion across the complete length of the tubesheet
zone with fissuring near the surface. The depth of through the entire wall thickness. The cracks
cracking was limited to approximately 1 mm. In- propagated in the longitudinal direction as well
spection of the circumferential welds in the pip- in as in the transverse direction of the tube. Ob-
ing was only possible by external manual UT- viously, the ferrule protection is not sufficient to
impulse-echo technique. In all welds, relatively completely prevent hydrogen attack damage in
pronounced indications were found. The inter- the tubesheet zone during long-term operation.
pretation of the results was problematic due to This damage scenario is particularly critical with
the excessive penetration on the root pass which regard to the restricted access to this zone be-
cannot be ground flush to the inner surface dur- cause there is no NDT inspection method availa-
ing fabrication. Therefore, it was impossible to ble to identify damages in an early state. Internal
determine whether the indications were caused leakages of synthesis gas into the feed water side
by weld imperfections or fissuring. For safety can only be identified by hydrogen control meas-
reasons, it was decided to remove all welds and urements in the steam outlet of the connected
weld repair by inserting new fittings. steam drum.
Before scrapping the “old” waste heat boiler
W722, some test pieces were removed for metal-
lographic investigations. The main focus was the
tube-to-tubesheet connection of the hot gas inlet
(syngas temperature approx. 480°C) coming
from the converter C702. The tubesheet was con-
structed out of 2.25Cr-1Mo-Steel with a Ni-
Base-Alloy (Ni 6082 / ERNiCr-3) weld-cladding Figure 11: Synthesis gas inlet of the waste heat
and heat-protected by a refractory lining. To pro- boiler W722
tect the tube-to-tubesheet welds and the uncooled
tube length in the tubesheet, ferrules constructed
of Ni-Base-Alloy 600 were inserted (Figure 11).
During cutting of the test pieces from the
tubesheet, it became obvious that some tubes
were separated from the tubesheet (Figure 12).
Closer metallographic examination made evident
AMMONIA TECHNICAL MANUAL 18 2014
Figure 12: Tube-to-tubesheet weld sample with a After 13 to 17 years in operation, no critical
circumferentially ruptured tube cracking in the circumferential welds of both
converters was observed. Therefore, the benefit
of the new design concept is proven. The find-
ings of internal inspection are consistent with the
external NDT results which show that the NDT
inspection concept for both converters is still ap-
propriate and able to identify cracking before it
becomes critical.
The unexpected severe damage that was found in
crevices and filet welds of the weldolets in the
piping suggests that the nitrogen diffusion into
the material is enhanced under stagnant condi-
Figure 13: Microsection of the tube-to-tubesheet tions. To verify this finding, test pieces contain-
weld (position “A” in Figure 12) ing crevices have been positioned in the synthe-
sis loop until the next turnaround in 2018. The
material for the test pieces was extracted out of
the inlet nozzle of the replaced waste heat boiler
to ensure accordant material properties.
Both heat exchangers in the syngas loop suffered
from a known problem of hydrogen attack in the
Figure 14: Microsection of the tube-to-tubesheet buffer welds which cannot be repaired in a prop-
weld (position “B” and “C” in Figure 12) er way. New damage aspects were discovered at
the tube-to-tubesheet connections of the scrapped
waste heat boiler. These problems clearly
Conclusions showed that the lifetime of these components is
In summary, the outcome of the inspection expe- limited and this must be considered in the risk
riences is that all components in the synthesis assessment.
loop are in some way affected by the combina-
tion of nitriding and HTHA. Most of these indi- Acknowledgment
cations are restricted to a maximum depth of ap-
prox. 2 mm measured from the inner surface. A The authors would like to thank the teams from
fitness-for-service analysis based on the inspec- operation and inspection for their contribution to
tion results showed that most of the findings are the turnaround 2013 and their input to this publi-
not critical yet, but must be monitored on a regu- cation.
lar basis with a comprehensive inspection con-
cept to prevent unexpected failure and to opti-
mize maintenance and replacement concepts
(Table 3).
2014 19 AMMONIA TECHNICAL MANUAL
Equipment Findings Operation Estimated Inspection Concept / additional Measures
Time in Remaining
Years Lifetime in Years
C701 Minor HTHA attack Regular external NDT monitoring
13 >10 (every 2 ½ years),
internal NDT during catalyst exchange
C702 Minor HTHA Regular external NDT monitoring
17 >10 (every 2 ½ years),
internal NDT during catalyst exchange
W721 Minor HTHA on shell, External UT wall thickness measurement,
severe HTHA on seal 30 >5 internal NDT of shell and
buffer welds diaphragm seal buffer weld
To be replaced during next TAR 2018
W722 Minor HTHA on shell, External UT wall thickness measurement,
severe HTHA on seal (18) >15 internal NDT of shell and
buffer welds and tube-to- diaphragm seal buffer weld,
tubesheet connections NDT monitoring of tube-to-tubesheet weld
impossible, leak detection via
Start-up of new in 2013 0 hydrogen control in steam,
spare part concept applied
Piping Minor HTHA in pipe 100% weldolet inspection included
W721-W722 material, severe HTHA in 30 >5 in TAR scope,
crevices of weldolets repair of all weldolets and all girth welds
Piping to be replaced during next TAR 2018,
monitor crevice HTHA with test coupons,
Piping No indications for HTHA 100% weldolet inspection included in TAR
W722-W723 in pipe material, 30 >10 scope,
hydrogen embrittlement in repair of all weldolets
weldolet
Table 3: Fitness-for-service evaluations for the components of the synthesis loop
Literature [5] Prescott, G.R.; Grotz, B.J.: Weld Zone
Cracks in Repaired 2 ¼ Cr-1 Mo Ammonia Con-
[1] Heuser, A.; Wagner, G.; Heinke, G.: Hydro- verter, Ammonia Safety Symposium, Vancouver,
gen Attack in 2.25Cr-1Mo-Steel below Nelson´s 1994
curve caused by Ammonia Synthesis Gas, Am-
monia Safety Symposium, Los Angeles, 1991 [6] Hecht A.: Time of Flight Diffraction Tech-
nique (TOFD) – An Ultrasonic Testing Method
[2] Heuser, A.: Repair of a Thick-walled Ammo- for all Applications?, NDTnet, Vol. 2, No. 9,
nia Synthesis Converter Containing a Leak, 1997
Ammonia Safety Symposium, Los Angeles, 1991
[7] Isselborn, S.; Guns, L.: Failure of Synthesis
[3] Walter, M.: Examination of Crack Formation Waste Heat Boiler by Rotating Ferrules, Ammo-
in Final Girth Seam of Ammonia Converter nia Safety Symposium, Orlando, 1993
R103 at Grand Paroisse – Comparison with Con-
verter C702 at BASF, Internal Report, 1993 [8] Bickel, W.; Walter, M.: Repair of Waste Heat
Boiler in Synloop of NH3-Plant, Ammonia Safe-
[4] Prescott, G.R.: Regarding Cracking within ty Symposium, Orlando, 1993
Reactor Vessels 101, 102, and 103 of the Am-
monia Synthesis Reactors of Société Grande
Paroisse, Toulouse, France, S.F. Braun Inc., Re-
port
AMMONIA TECHNICAL MANUAL 20 2014
