High Pressure Piping Safety

Incidents in Urea Plants

High pressure piping is often an area which receives less attention during the lifetime of a urea plant;
there is no logical reason for this. Paying not enough attention or wrong inspection/repair procedures
can lead to catastrophic incidents. This presentation will provide an overview of the different
corrosion phenomena occurring in high pressure piping systems in urea plants. It will elaborate the
corrosion phenomena from the inside (process side) as well as the outside (atmospheric corrosion /
corrosion under insulation). Many practical cases will illustrate the risks involved and will show the
importance to pay sufficient attention to this part of the urea plant.

Mark Brouwer
UreaKnowHow.com

Giel Notten
NTT Consultancy

C
orrosion phenomena of high pressure pip-
ing can be both from the process side as
well as from the outside. Both are impor-
tant and can be risk to assure the integrity
of high pressure pipe Line system in urea plants.
Process side
Urea is formed in a modern urea plants according
to the following two-step reaction scheme:
Formation of ammonium carbamate:
2NH3 + CO2 ⇔ NH2COONH4 + a cal
Dehydration of ammonium carbamate to urea
NH2COONH4 ⇔ H2O + NH2CONH2 - b cal
It is ammonium carbamate which is the corrosive
component in the urea plants especially at higher
pressures and higher temperatures.
In urea plants typically austenitic stainless steels
such as 316L urea grade or 25-22-2 are applied as
the material of construction for high pressure pip-
ing systems; these materials can experience corro-
sion in the presence of ammonium carbamate. Two
principle types of corrosion need to be distin-
guished: 1) passive corrosion and 2) active corro-
sion.
Passive corrosion is taking place always and any-
where when carbamate is in contact with stainless
steels in the presence of oxygen; it is in fact the

2010 95 AMMONIA TECHNICAL MANUAL

 formation of a passive chromium oxide layer on
the surface which protects the stainless steel. As
the oxide layer dissolved in the solution, continu-
ously new oxygen need to be added to rebuild the
passive layer and thus continuously a certain over-
all corrosion rate is taking place, typically between
0.02 and 0.1 mm/year depending on the tempera-
tures, carbamate concentration, oxygen content etc.
This passive corrosion does not form a threat to the
integrity of the equipment and materials as this
kind of corrosion is incorporated in the design.
Maybe only in older urea plants (>20 years) regu-
lar inspections need to confirm sufficient margins
are available to assure the integrity of the applied
materials.
More dramatic is the situation when for example
the oxygen is not present anymore or when tem-
peratures are too high. In that case the oxygen
layer cannot be assured anymore and active corro-
sion starts with significant higher rates such as 30
to 60 mm/year. No design margins are available for
active corrosion phenomena and specific attention
need to be paid during the design, construction and
operation of any urea plants to avoid active corro-
sion.
The pictures above show examples of passive and
active corrosion in a urea plant. Passive corrosion
(left) one can recognise by blue/reddish/brown
colours indicating the oxygen layer. Active corro-
sion (right) however gives a shiny surface which is
AMMONIA TECHNICAL MANUAL
many times locally present, sometimes even with
locally a significant reduction of the wall thick-
ness.
In the high pressure pipelines of a urea plant active
corrosion is in most of the cases caused because
not enough oxygen is present to assure a passive
layer.
For example between a flange connection a crevice
can exist when the two flanges are not connected
in a correct way as shown in the figures above. In
this crevice the carbamate solution is stagnant.
Oxygen in the carbamate solution is slowly con-
sumed because of the passive corrosion, after a
certain period active corrosion will start leading to
a leak and damage of the flange face.
The pictures above show another corrosion phe-
nomena, which occurs easily in gas phase high
pressure pipelines of urea plants is condensation
corrosion. Carbamate containing gas condenses
against cold spots and the liquid carbamate does
not contain any oxygen so active corrosion readily
starts.
96 2010
 It is good practice to trace and carefully insulate
gas phase high pressure lines to maintain a temper-
ature higher than 307°F (153°C), which is the max-
imum condensation temperature of carbamate.
However damaged insulation or wrong design de-
tails can cause cold spots leading to condensation
corrosion as is shown in the pictures below.
Further with austenitic stainless steels one has to
pay proper attention to chlorides as these can cause
chloride SCC. Using glue or paint containing chlo-
rides can cause already trans-crystalline cracks as
in the flange face indicated in the picture below.
In the urea high pressure synthesis section at sev-
eral areas the pressure drops and velocities are
high causing erosion corrosion as a passive layer
cannot be maintained under these circumstances.
2010
Sensitive areas are valve bodies, stems and bends
when not designed in a proper manner (refer to the
pictures above).
Finally dead points or other areas where stagnant
flow can occur are points of attention as in these
stagnant flow zones the refreshment of oxygen
cannot be guaranteed leading again to a risk for ac-
tive corrosion. The pictures below show two ex-
amples of this type of corrosion.
The reported case during the Ammonia Safety
Conference 2009 of Yara Canada of corroded drain
line is also an example of this type of corrosion. A
similar incident occurred last year in a Chinese
urea plant and likely many other cases did occur
but have not been reported.
Atmospheric corrosion / Corrosion Under
Insulation
Also corrosion phenomena from the outside can
risk the integrity of high pressure pipeline systems
in urea plants. During asset lifetime studies in urea
and ammonia plants several times quite severe ex-
ternal corrosion was encountered. Corrosion under
insulation as one of the key items for further de-
tailed investigation as it is the most significant
concern for safety and costs of the piping systems,
because it has the potential to affect a large amount
of piping containing ammonia gas and liquid.
Moisture is here a key pre-condition for this kind
of corrosion to take place, without moisture no cor-
rosion.
There are many ways moisture can penetrate the
insulation:
• Rain water
97 AMMONIA TECHNICAL MANUAL
 • Vapor resulting from “breathing” due to
cyclic temperature changes, followed by
dew formation
• Increased water exposure resulting from:
- nearby cooling towers
- water-jetting of heat exchangers
- fire-fighting drills
- sprinkler installations
- leaking trace lines
The figure and picture above show examples of
There are two main types of atmospheric corrosion critical areas for corrosion under insulation on an
(or corrosion under insulation): isometric and in practice.
1) Overall corrosion and
2) Stress corrosion cracking (SCC). SCC is another corrosion phenomena often found
in ammonia/urea complexes. The following com-
Overall corrosion is maybe a somewhat misleading binations are important to pay attention to:
name as this kind of corrosion is a crate type attack • carbon steel - nitrate ions
of the material and is occurring only at critical • austenitic stainless steel - chloride ions
areas such as: • copper/zinc alloys (e.g. brass) – ammonia
• Damage to and/or leaks (e.g. faulty over-
lap) in insulation jacketing; Cracks caused by SCC are more difficult to see and
• Bends at the low end of vertical pipelines; may result in rupture before leak rather than leak
• T-joints; before rupture and therefore are more critical to as-
• Supports and passages through the insula- sure the integrity of the piping and equipment. Ni-
tion jacketing; trate SCC in carbon steel is inter-granular of na-
• Initial and end points of the insulation par- ture. Chloride SCC in stainless steels as well as
ticularly for vertical pipelines; NH3 SCC in brass are typically trans-granular of
• Drains (dead line sections such as sampling nature. To initiate SCC in stainless steel and car-
points) and vent pipelines; bon steel, moisture needs to be present and tem-
• Location relative to, for instance, cooling peratures should be higher than 122°F (50°C). NH3
towers (in the prevailing wind direction); SCC in brass is already likely to occur at ambient
• Areas where apparatus is cleaned by water- temperature.
jetting;
• Apparatus and pipe line systems with
sprinkler systems;
• Apparatus and pipe line systems affected
during fire-fighting drills;
• Lowest point of sloped pipeline;
• Insulation covers of valves and fittings;
• Damaged fire proofing (including water
deflectors);
• Field welds and welds in lines requiring in-
spection by authorized inspector;
• All areas where any abnormality is ob-
served, such as rust, moss growth, ice;
• Leaking trace lines.

AMMONIA TECHNICAL MANUAL 98 2010

 Cases The figure below shows the location on the failed
weld-o-let.

Catastrophic failure of a weld-o-let

Figure 2: Location of failed weld-o-let
Chemical accident in the urea plant A more detailed investigation showed corroded
of a fertilizers industry - failure of areas in the Heat Affected Zones of the welds (fig-
weldolet resulting in death of four ure 3)
persons.
There was a chemical accident in
Figure 3: Corrosion in the Heat Affected Zones of
the Urea Plant at …. in 2000. An 8" the welds
dia high pressure pipe line housing a
weldolet was connected between Picture 9 a/b: weld-o-let (left) and corrosion in
autoclave (urea reactor) of 108MT HAZX zones (right)
capacity and the stripper to carry
ammonium carbamate (Urea
Solution). …. On that day in 2000, a The investigations also showed inter-crystalline
substantial quantity of ammonium corrosion in these Heat Affected Zones as indi-
carbamate solution leakage was cated in the figure and pictures below.
noticed at the weldolet joint of the
pipeline. A maintenance manager
along with two operators, an
engineer and two contract workmen
were trying to plug the leakage by
providing a proper clamping. In the
process, the weldolet joint gave way
resulting in sudden release of
pressurized hot ammonium
carbamate solution. As a result, the
personnel on the job were exposed
to hot solution and toxic gas.
Consequent to which, 8 persons
were affected amongst them 2 died
on the spot and the other two at the
hospital amounting to death of 4
persons including the maintenance
manager and an engineer.1)

The leak occurred in a 316L urea grade high pres-

sure pipe line going from the Reactor to HP strip-
per. During installation of a clamp, the weld-o-let
ruptured. Four people died and four other people
got injured. The catastrophic failure occurred after
24 years on-stream time and resulted that the plant
had to shut-down for two months.

2010 99 AMMONIA TECHNICAL MANUAL

 Overall corrosion of a high pressure CO2 pipe
line
For example a carbon steel high pressure CO2 pipe
line with an operating pressure of 140 bar and op-
erating temperature of 158°F (70°C) was insulated
and ruptured at the lower part of vertical pipe line
near the bend. This happened after 25 years on-
stream time.

Investigations showed that the cause of failure

were two-fold:
1) Inferior material quality: The chromium
content of the weld-o-let was only 15.3%,
while the minimum required Chromium
content of 316L urea grade material is The pictures above show corrosion under insula-
17.0%. tion of a high pressure CO2 line (left), clearly
2) Insufficient refreshment of carbamate solu- showing the crater type attack (right). Also insu-
tion in T-joint will increase the corrosion lated carbon steel pipe lines with an operating tem-
rate. perature of 158°F (70°C) needs a coating and in
Note: Applying a clamp to stop a leak is dangerous these kind of cases personal protection instead of
as it creates a crevice where active corrosion can insulation would have been a better choice.
start leading to a potential bigger catastrophe.
Overall corrosion of a High Pressure
Besides several general safety lessons, like per- ammonia pipe line
forming safety training and wearing personal pro-
tection, the following specific lessons were to be Another example is a carbon steel high pressure
learned: ammonia pipe line, where overall corrosion was
1) Assure the quality of the applied materials taking place behind a clamp. After 21 years on
fulfils the minimum requirements; stream time the original wall thickness reduced
2) Assure the quality of the installation and from 11 to 6 mm, which is below the required min-
welding services; imum wall thickness.
3) Perform proper inspections and testing dur-
ing installation and after repair procedures
(hydrotest, X-ray test of weld-o-let);
4) Perform regular corrosion inspections of
critical areas especially in plants older than
20 years;
5) Never apply a clamp on a carbamate con-
The pictures above show the overall corrosion be-
taining pipeline.
hind a clamp of a high pressure ammonia line
(left), leading to a critical reduction of the wall
thickness over a significant length (right).

The severe decrease in wall thickness (from 11 to 6

mm) of the carbon steel high pressure ammonia

AMMONIA TECHNICAL MANUAL 100 2010

 line is due to corrosion in crevice in the area of the The next picture shows the cracks caused by chlo-
clamp; at this location a protective coating was not ride SCC as result of this situation.
applied or completely damaged. The corrosion oc-
curred as a result of wetting during flushing the
floor.

We would like to recommend applying a protective

coating system on the pipeline also in the area of
the clamp. For example apply a glass-fiber tape be-
tween the pipeline and the clamp and avoid / be
aware of wetting of the pipeline during flushing the
floor.

Stress corrosion cracking

Many incidents of SCC are known and reported in
literature. The trans crystalline cracks form a vi- What causes this failure ?
cious kind of failure mechanism as the loss of inte-
grity can come by surprise. In the high pressure In presence of moisture and air the following cor-
pipeline system of a urea plant the most common rosion reactions take place:
critical combination is austenitic stainless steel
with chloride ions, especially in plants in coastal 4 Fe -> 4 Fe++ + 8e
areas. 2 O2 + 4 H2O + 8e -> 8OH-
4 Fe++ + 8 OH- -> 4 Fe(OH)2
The reported incidents show that the sources of 4 Fe(OH)2 + O2 + 2 H2O -> 4 Fe(OH)3
chlorides are not always obvious and one should 4 Fe(OH)3 -> Fe2O3.H2O + 2 H2O
realize that small quantities can cause already
problems. In presence of contaminants chlorides the corro-
sion rate is accelerated due to decrease of pH. The
A less obvious example of chloride SCC is when a chemical reactions involved in presence of chlo-
carbon steel steam tracing touches a stainless steel rides are:
pipeline as can be seen in the picture below.
Fe++ + 2 Cl- -> FeCl2
FeCl2 + 2 H2O -> Fe(OH)2 + 2 HCl

The pH will decrease, which increases the risk of

chloride SCC. Other pre-conditions are the pres-
ence of oxygen, chlorides, tensile stresses and a
temperature above about 122°F (50°C).

Another example with a larger pipeline is pre-

sented in next picture. A carbon steel pipeline sup-
port is touching a stainless steel pipeline.

2010 101 AMMONIA TECHNICAL MANUAL


The next picture shows the crack formation as a re-
sult of the combination of chlorides, moisture,
higher temperatures and carbon steel clamp touch-
ing an austenitic stainless steel pipeline.
Measures to increase the reliability
and integrity of high pressure
pipeline systems
9 Strict control of the quality of materials of
construction applied in high pressure sec-
tion (high pressure piping) of a urea plant
is critical.
9 Strict control of the quality of installation
and welding of high pressure piping is crit-
ical.
AMMONIA TECHNICAL MANUAL
9 It is never allowed to install a clamp on a
leaking high pressure pipeline in urea
plants as it results in risks of active corro-
sion due to crevices formed.
9 Stagnant conditions of carbamate fluids
should be avoided (remove “dead” line sec-
tions which are not in use anymore).
9 Pay attention to proper tracing / insulation
of gas lines.
9 Atmospheric corrosion is a serious threat to
the safe operation of, especially older, urea
plants (or any other petrochemical plant).
9 If a hazardous situation might arise or if
there is a risk of production outage, preven-
tive / predictive maintenance with respect
to external corrosion, should be carried out
rather than breakdown maintenance.
9 Conditions promoting atmospheric corro-
sion as well as requirements regarding pre-
ventive measures should be laid down in
adequate standards.
9 Application of painting systems and insula-
tion systems if necessary should be per-
formed according to the requirements in
these standards regarding product quality
as well as guidance and control.
9 It is essential that management is aware of
the risk and consequences of internal and
atmospheric corrosion of high pressure
pipelines in a urea plant. That awareness
should be transferred to the workforce via
communication programmed, training and
a detailed corrosion control plan.
Conclusions
High pressure piping is often an area which rece-
ives less attention during the lifetime of a urea
plant; there is no logical reason for this. Paying not
enough attention or wrong inspection/repair proce-
dures can lead to catastrophic incidents.
This paper provides an overview of the different
corrosion phenomena occurring in high pressure
piping systems in urea plants, elaborating the cor-
102 2010
 rosion phenomena from the inside (process side) as
well as the outside (atmospheric corrosion / corro-
sion under insulation).

Many practical cases illustrate the risks involved

and will show the importance to pay sufficient at-
tention to high pressure pipelines of a urea plant. It
is very important to involve reliable companies,
with specific experience in urea, in the engineer-
ing, supply, installation and corrosion inspections
of high pressure pipelines in urea plants.

Literature
2009 05 Brouwer UreaKnowHow.com Chlorides
in Urea Plants, www.ureaknowhow.com.

2009 06 Notten NTT Consultancy UreaKnow-

How.com Forms of Atmospheric Corrosion,
www.ureaknowhow.com.

2009 07 Notten NTT Consultancy UreaKnow-

How.com Conditions promoting Atmospheric Cor-
rosion, www.ureaknowhow.com.

Corrosion Engineering Guide.

By Giel Notten; NTT Consultancy
Published by KCI Publishing B.V; October 2008.
ISBN 9789073168299.

2010 103 AMMONIA TECHNICAL MANUAL

AMMONIA TECHNICAL MANUAL 104 2010