Catastrophic failure and

near misses in urea plants

due to corrosion
30th AFA Fertilizer technology
Conference
Alex Scheerder, Stamicarbon

10-12 October 2017

[Sheraton Hotel Amman, Jordan]

The innovation & license company

of Maire Tecnimont.
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Catastrophic failure and near misses in

urea plants due to corrosion

Author Alex Scheerder

conference name 30th AFA Fertilizer technology Conference

conference date 10-12 October 2017
date paper August 31, 2017
revision Final
classification PUBLIC INFORMATION | authorized
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of Maire Tecnimont.

CONTENTS

1. Abstract 4

2. Introduction 4

3. Case history 1: catastrophic failure of a hp scrubber 5

3.1. Root cause analysis 6
3.2. failure of Leak detection sysyem 8
3.3. summary of case history 1 8

4. case history 2: catastrophic failure of a urea reactor 8

4.1. technical data urea reactor and case history 9
4.2. investigation of root cause 10
4.3. summary of case history 2 11

5. Case history 3: near miss urea reactor 11

5.1. leak detection system 12
5.2. investigation 12
5.3. summary of case history 3 14

6. Conclusions 14

7. references 14
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1. ABSTRACT

One of the challenges in operating a urea plant is to combat the corrosive process environment in the
high pressure synthesis section. To protect the pressure vessel a corrosion resistant barrier is applied.
The reliability and safety depends on the choice of the stainless steel, the fabrication methods, quality of
welding and last but not least inspections and maintenance during the total life cycle. Any weakness in
the protective barrier, either introduced during fabrication or during operations will increase the risk of
(catastrophic) failure.
This paper will present three cases of failures and near misses which are related to corrosion from
process side. The learnings from these mishaps are the basis of Stamicarbon philosophy to safely
operate the critical high pressure urea equipment.
Needless to mention that apart from process related corrosion, the urea equipment faces also corrosion
threats from outside, i.e. atmospheric corrosion and corrosion under insulation. Also corrosion and
failures in HP urea piping is not subject of this paper. For the interested reader, reference is made to
other publications [1], [2] and [3].

2. INTRODUCTION

Ammonia and carbon dioxide are used as feedstock in a urea plant. The reactions take place at relative
high pressure and as an intermediate reaction step ammonium-carbamate is formed. This ammonium-
carbamate is highly corrosive to carbon steel and therefore the pressure vessels are protected against
corrosion by applying a corrosion resistant barrier. All parts that comes in contact with the process
(liquid or gas phase) needs to be protected. The protective layer can be a weld overlay or a liner.

In the past austenitic stainless steels like 316L UG and X2CrNiMo25-22-2 are used in Stamicarbon
plants. Nowadays a more resistant duplex stainless steel Safurex® is applied. The paper will discuss
cases were austenitic stainless steels are applied. This is only possible when passivation air is added to
the process. Passive corrosion rates are in the range of 0.05 to 0.1 mm/y. When losing the passivation
air also these austenitic stainless steels will corrode severely; active corrosion rates can be as high as 30
mm/y or even higher.
Corrosion of the barrier steel might result in a perforation, allowing the ammonium-carbamate to come
in contact to the underlying carbon-steel. Corrosion rates of up to 500 mm/y are reported and this will
impair the integrity of the pressure vessel in a relatively short period of time.
By all means leakage of ammonium-carbamate needs to be avoided during operations and any leaks
needs to be stopped immediately.
Stamicarbon has developed stringent requirements to minimize the risk for and consequences of
carbamate leakages. This entails the choice of corrosion resistant materials, the fabrication methods (i.e.
welding procedures), implementation of leak detection system, guidelines how to start-up and run the
plant, maintaining sufficient passivation air and last but not least, regular inspection and maintenance.
Despite these precautions, catastrophic failures still occur, however scarcely. Three case histories are
presented.

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3. CASE HISTORY 1: CATASTROPHIC FAILURE OF A HP SCRUBBER

The first case describes an incident in a Stamicarbon CO2 stripping plant. The incident occurred in 1998
after 17 years of operation.
Two days after a normal maintenance shutdown, the high pressure Scrubber ruptured at 04.30 hr in the
morning. The HP Scrubber, designed with a cylindrical dome (see figure 1) is located high up in the urea
plant, see figure 2. The plant was running normal and fortunately nobody was present in the plant at the
time of the rupture.
Stamicarbon was requested to assist in the root cause analysis of this failure.
The top part of the HP Scrubber was ruptured and completely disconnected from the vessel. One part of
the rupture disk was found back outside the urea plant site. Also surrounding equipment, piping and
concrete structure were damaged, see figure 3.
The function of the HP Scrubber is to remove inerts from the process gas. The ammonia and carbon
dioxide are condensed and reused in the synthesis loop. The inerts are vented to the atmosphere. In the
dome part of the HP Scrubber the presence of an explosive mixture of H 2, NH3 and air is possible.
Therefore the dome part is designed such to avoid any loss of containment in case of an explosion.

Figure 1: HP Scrubber with cylindrical dome in multi-layer design. Rupture disk closes the dome area
at the bottom.

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Figure 2: Location of HP Scrubber Figure 3: damaged top part of HP Scrubber and

surrounding structure

3.1. ROOT CAUSE ANALYSIS

Initially two possible root causes were identified:
1) An explosion due to an explosive hydrogen/ammonia/air mixture in the HP Scrubber in
combination with a loss of mechanical integrity of the scrubber dome.
2) Deterioration of the mechanical integrity of the scrubber dome and subsequent failure under
operating conditions.

3.1.1. POSSIBLE ROOT CAUSE 1: EXPLOSIVE MIXTURE

The gas composition present in the HP Scrubber just before the rupture was analyzed and the mixture
was not within the explosive range as is presented in figure 4.

Figure 4: Gas composition in HP Scrubber just before the rupture; in the save range

Therefore it was concluded that no explosion occurred because:

 Prior to the rupture the operating point is outside the explosion triangle
 The process condition were stable and normal
 No other plant disturbances occurred

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3.1.2. POSSIBLE ROOT CAUSE 2: MECHANICAL DETERIORATION OF DOME

The dome part consists of a cylindrical multi-layer carbon steel pressure shell lined with 316L-UG liner
(WT = 6 mm). The hemispherical part is a solid-wall design also lined with 316L-UG.
The cylindrical part is constructed of 4 layers of 9 mm K-TEN steel (K-TEN quenched and tempered
steel with tensile strength: 62 Kg/mm2 and a minimum yield strength of 45.3 kg/mm2 at design
temperature of 185 °C).
The cylinder part was ruptured in longitudinal direction; the three inner c-steel layers were through wall
corroded, see figure 5, whereas the outer (fourth layer) was only minor attacked.

Figure 5: severe corrosion of three Figure 6: backside of liner plate with carbamate
inner c-steel layers corrosion

The corrosion is due to ammonium-carbamate leaking through the leak in the liner. Carbamate
corrosion is visible at the backside of the liner, see figure 6. A cover plate was welded onto the liner at
the location of the leak. The leak path was developed along a weld defect in the filet weld of the cover
plate, see figure 7.

Figure 7: leak path via fillet weld of cover plate and leak detection hole towards the multi-layered
pressure shell.

The fracture surfaces shows plastic deformation at 45° –angles; this indicates fracture by shear stresses
under mechanical overload (due to the thinning) resulting into collapse of the dome. This excludes
rupture by explosion.

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Hidden defects in fillet welds of cover plates are likely to occur. Therefore Stamicarbon is not in favor for
installing cover plates.

3.2. FAILURE OF LEAK DETECTION SYSYEM

The HP Scrubber was equipped with a leak detection system. During transport from the manufacturer
shop to the plant site the leak detection holes are plugged to avoid ingress of debris and moisture.
However during the commissioning of the HP Scrubber one of the leak detection hole was not opened
and connected to the system, see figure 8. Therefore the leak in the cover plate was unnoticed and
corrosion of the pressure shell could commence.

Figure 8: hemi-head part of dome with plugged LDS hole (P-5).

3.3. SUMMARY OF CASE HISTORY 1

 The HP scrubber did not fail due to an explosion, but due to unnoticed corrosion of the c-steel
pressure shell.
 Ammonium-carbamate corrosion occurred in the gas filled dome of the HP Scrubber. Due to
improper insulation/tracing, condensation of the gasses created the corrosive solution on the
inner surface of the dome.
 Corrosive ammonium-carbamate was leaking trough a hidden weld defect in a fillet weld of a
cover plate on the liner.
 Hidden defects are likely to occur in fillet welds of cover plates. Stamicarbon is not in favor for
installing cover plates, also not for local repairs.
 It is of paramount importance to have an effective, good working leak detection system in place
as a last barrier of defense to avoid catastrophic failures.

4. CASE HISTORY 2: CATASTROPHIC FAILURE OF A UREA REACTOR

The urea reactor of a small conventional urea plant suddenly ruptured during normal operations. The
plant was commissioned in 1969 and the incident occurred in 1992, after 23 years of operation. The
reactor ruptured almost half way the cylindrical part and the crack propagated in circumferential
direction. The top part of the reactor was launched and dropped several hundred meter away from the
plant site. The bottom part was catapulted partly into to ground, see figure 9. Fortunately no people
were killed.

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Figure 9: overview of plant site (left) and ruptured urea reactor (right)

4.1. TECHNICAL DATA UREA REACTOR AND CASE HISTORY

The reactor has a cylindrical part in so-called multi-layer design with a length of 25 m and diameter of
1.6 m. The hemi-head in top and bottom are solid wall design and the reactor is lined with a 316L UG
liner (6 mm). Original the top and bottom hemi-head are overlay-welded (12 mm).
The reactor is equipped with a leak detection system in the cylindrical part as shown in figure 10.
Three leak detection holes are located close to the circumferential liner welds (500 mm) and 120° apart
in circumferential direction.

Figure 10: Schematic overview urea reactor with liners and position of leak detection holes along the
circumferential liner welds.

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Through the years, repairs have been done on the liner and overlay welding. Also modifications were
made on the leak detection system.
A first major repair of the reactor was done in 1984 (after 15 years of operation). The weld overlay in the
hemi-heads were severely corroded and these were lined (including installation of a leak detection
system).

In 1989 (20 years after commissioning) a first leak was detected at the circumferential weld C5 and
plant management decided to stop the plant and repair the leak. Several repair were carried out on this
occasion.

In January 1992, a brownish substance was detected emerging from a leak detection hole at
circumferential weld C7. Plant management however made the decision not stop the plant. It was
assumed that this substance was originating from the leak in 1989, which occurred two and half years
back and at a different location (C5).

June 1992, some white product came out of leak detection hole near circumferential weld C5. Again the
pant was not stopped to attend the leak.

July 1992, the urea reactor failed catastrophically.

4.2. INVESTIGATION OF ROOT CAUSE

Investigation of the c-steel multi-layer pressure shell clearly indicated that the strength of the layers was
compromised by severe corrosion which resulted in wall thinning, see figure 11 and 12. This resulted in
too high stresses in the shell due to the internal pressure which triggered the catastrophic failure of the
reactor shell.
The corrosion started clearly underneath the liner and not from the outside (atmospheric corrosion or
corrosion under insulation).
The leak spot was identified at one of the tray clips, see figure 13. The reactor trays are supported by
clips welded to the liner. Despite the design rule, to weld the tray clips with full penetration welds, the
said clips welds were of poor quality and showed lack of fusion defects, see figure 13 and 14.

Figure 11: ruptured shell part Figure 12: severe corrosion of c-steel layers

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Figure 13: poor weld quality of tray clips Figure 14: lack of fusion defects; active corrosion in
cavity

Due to the poor weld quality, carbamate corrosion created a leak path into the cavity underneath the
clip. In this cavity active corrosion started due to depletion of oxygen. The active corrosion created a leak
path through the liner, to allow the carbamate to come in contact with the c-steel pressure vessel. In a
relatively short period of time (6 months) the reactor ruptured.

4.3. SUMMARY OF CASE HISTORY 2

 Poor weld quality of the tray clips attached to the liner is the root cause of this catastrophic
failure.
 The poor weld quality resulted in lack of fusion defects, which triggered active corrosion of the
liner.
 The leak in the liner was noticed via the leak detection hole, but no action was taken by plant
management to stop the leak.
 As a consequence the c-steel multi-layer was corroded in a relatively short period of time,
resulting in catastrophic failure.

5. CASE HISTORY 3: NEAR MISS UREA REACTOR

This case occurred in the urea reactor of a CO2 stripping urea plant commissioned in 1994. The urea
reactor is a solid wall design (112 mm wall thickness in cylindrical part) with a 316L UG liner (8 mm
thickness). The incident occurred in 2015 after 21 years of operations. A catastrophic failure was
prevented by alert action of the plant operator, while the installed sophisticated leak detection system
failed.
During his daily routine plant tour the plant operator observed in the morning (08:30 hrs) crystallized
white product deposited on the insulation sheeting of the urea reactor, see figure 15 which aggravated
quite quickly in time. Also some ammonia vapor was noticed.

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November 05 08:30h 2015 November 05 12:30h 2015

Figure 15: Crystalized product visible on cover sheeting insulation urea reactor

Initial it was assumed a leak at the man-way cover, since the leak detection system was not indicating
any leak.
A closer look however indicated a possible leak in the liner and the plant was stopped for inspection.

5.1. LEAK DETECTION SYSTEM

In 2006 a state-of-the-art leak detection system was installed to monitor all high pressure urea synthesis
equipment in this plant. The principle of the leak detection system is to circulate dry air behind the liner
compartments of all connected equipment and to analyze the received air for presence of ammonia. The
principle is schematically presented in figure 16. The leak monitor is connected to the DCS system in the
control room.

HP stripper Header/cooler

Poolcondenser Header/cooler
Central /
Header
Reactor Header/cooler

HP scrubber Header/cooler

Ammonia
remover
Leak
monitor

Instrument
Off-gases
air

Figure 16: principle of leak detection system, circulating dry air to all connected equipment.

5.2. INVESTIGATION
The leak detection pipes connected to the suspected area of the urea reactor were disconnected and the
presence of ammonia was confirmed in the leak detection hole.

After opening the urea reactor, the leak was easily identified. The leak was located in the circumferential
weld between the original 316L UG liner (brown surface lower part figure 17) and the X2CrNiMo25-22-2
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liner (grey upper part in figure 17) which was installed in 2002. Relining the top part of the reactor was
necessary due to corrosion problems.

Figure 17: leak found in the circumferential weld between the X2CrNiMo25-22-2 relined part (top)
and original 316LUG liner

In order to access the integrity of the c-steel pressure shell a window was cut from the liner around the
leak point, see figure 18. Corrosion of the c-steel vessel wall was evident. Wall loss ranged between 10
and 30 mm. In one local area (80 x 50 mm) a maximum wall loss of 58 mm was found (remaining
thickness 50 mm; original 112 mm), see figure 19.

Figure 18: corrosion of the c-steel pressure shell visible Figure 19: maximum corrosion depth:
58 mm

It was decided to make a temporarily repair and to execute a full repair later on, which was executed
successfully within 1 year. The integrity of the reactor is restored again.

5.2.1. LEAK DETECTION SYSTEM

The pinhole leak in the liner created severe corrosion attack of the c-steel pressure shell and the reactor
was put out of service just in time. The state-of-the-art leak detection however failed to indicate the leak;
this was due to a combination of wrong commissioning of the system and failure of some components;
thus insufficient inspection and maintenance of the system.
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The leak detection system was refurbished and made operational before start-up of the plant.
Also an inspection and maintenance program was implemented to increase the reliability and
availability of the system. All plant operators were instructed again.

5.3. SUMMARY OF CASE HISTORY 3

 The root cause of the near miss is a small leak in the liner weld.
 The leak was not indicated by the leak detection system, since it not working properly
 Catastrophic failure was avoided by an alert action of a plant operator.
 Plant management took immediately the correct decision to stop the plant
 Safe operations of the plant is only possible with a good working leak detection system.

6. CONCLUSIONS

The three case histories demonstrates the risks that come with the high corrosiveness of the
ammonium-carbamate. Ammonium-carbamate is formed in an intermediate step in the production of
urea from ammonia and carbon dioxide. To protect the pressure vessels from corrosion a stainless steel
barrier is applied at the inside. In case of a liner, the liners need to be checked continuously for any leaks
by a leak detection system. It is of paramount importance to have a proper working leak detection
system in place and to act immediately upon a leak indication.
Furthermore it is demonstrated that the stainless steel barriers as well as all attachments needs to be
welded with high quality. Poor weld quality can lead to catastrophic failure. Therefore Stamicarbon has
stringent requirements with respect to weld quality of the stainless steel barriers in the critical high
pressure equipment. Stamicarbon also keep close control on the weld quality during fabrication.
Finally periodic inspections and maintenance is of importance. Adequate repair procedures can lower
risks for future corrosion problems.
For more than 50 years Stamicarbon gained experiences and knowledge on corrosion and repair of these
critical high pressure equipment and offers these services to the benefits of urea producers.

7. REFERENCES

[1] Safeguarding Stamicarbon’s High Pressure Urea Vessels.

AIChE Ammonia and Related Facilities Safety Symposium, San Francisco, CA USA, 2010
Alex Scheerder, Stamicarbon, The Netherlands

[2] To minimize Risks of Catastrophic Failure in Urea Plants Process Lines Requires RBI Methods.
AIChE Ammonia and Related Facilities Safety Symposium, Chicago, IL USA, 2012
Alex Scheerder, Stamicarbon, The Netherlands

[3] Operating Urea Plants with Small leaks Poses Potential Safety Risks.
AIChE Ammonia and Related Facilities Safety Symposium, Vancouver, BC, Canada, 2014
Alex Scheerder, Stamicarbon, The Netherlands

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P.O. Box 53 - 6160 AB Geleen,
The Netherlands.

Tel. +31 46 4237000

Fax +31 46 4237001

communication@stamicarbon.com
www.stamicarbon.com

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