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P A P E R

2 C

High-Pressure Zirconium
Urea Stripper

GUILLERMO BARTELLI

ABSTRACT

PRODUCTION SUPERINTENDENT
Profertil S.A. Argentina
Puerto Ingeniero White
Zona Cangrejales
B8103 Bahia Blanca, Buenos Aires
Argentina
T: 54 29 1453 3527
E: gbaratel@profertil.com.ar

Profertil, an Argentine company

equally owned by Agrium Inc. and
Repsol-YPF S.A., is located in
Ingeniero White, Baha Blanca,
Argentina. This plant has a name
plate production capacity of 2050
mt/day of ammonia and 3250
mt/day
of
urea
and
was
commissioned in January 2001. The
ammonia plant is a Haldor Topsoe
design; the urea plant is a
Snamprogetti design (now known as
Saipem SpA). The production plant
represented the largest design
capacity for any single train
ammonia or urea plant operating in
the world at that time. Maximum
production achieved has been 2278
mt/day for ammonia (~12% above
name plate design) and 3719 mt/day
for urea (~14% above name plate
design). Figure 1 shows an aerial
view of the Profertil fertilizer complex
in Bahia Blanca, Argentina.
Within the first year of start-up,
Profertil suffered severe corrosion to
the stainless steel alloy wetted
internals (310MoLN UNS S31050
also known as 25-22-2 Stainless
Steel) of a critical vessel (the urea

Co-authors

PIETRO MANTOVANI
Officine Luigi Resta SpA

GIANPIETRO TESTA
Saipem SpA

DON TIMBRES
D&E Consulting Inc.

RICHARD SUTHERLIN, PE
ATI Wah Chang

B.J. SANDERS
B.J. Sanders and Associates Inc.

JORGE VERSACE
Profertil S.A. Argentina

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stripper) in the urea plant causing

major losses in production. At that
time and after several repairs
Profertil decided to replace the urea
stripper with one of a different
construction material.
When Profertil initially reviewed
potential construction materials for
urea strippers, they found, based on
laboratory and field experience,
zirconium had excellent performance
in chemical processing applications,
including the urea environment.
During the next few years working
with Agrium, Snamprogetti (Saipem
SpA), Officine Luigi Resta and ATI
Wah Chang, Profertil was able to
specify zirconium as their material
of choice for the wetted internals for
a new urea stripper, and
successfully procured and installed
such a urea stripper for use in their
facility in 2007.
The choice for using zirconiumlined equipment and solid zirconium
tubes for this urea stripper entailed
significant research and a nonconventional design. This paper will
review the process used in selecting
zirconium, developing a specific heat
exchanger design and fabrication of

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2C HIGH PRESSURE ZIRCONIUM UREA STRIPPER

this urea stripper. This paper will also

review the operating experience and
success achieved after nearly three
years in service.

Figure 1. Aerial view of the Profertil fertilizer complex.

KEYWORDS

zirconium
urea production
urea stripper
Omegabond
Zircadyne
stainless steel
organic acids
mineral acids
ammonia
heat exchanger
chemical process industry
UNS S31050

INITIAL CORROSION
PROBLEMS

INTRODUCTION
The high-pressure urea stripper
exists in one of the most severe
process conditions in the urea plant.
The urea stripper is a vertical heat
exchanger (falling film evaporator)
which operates under high
temperatures and pressures.
Historically, a number of material
solutions have been applied to the
Snamprogetti (Saipem SpA) urea
stripper design. Because of the
severe corrosion experiences with
urea strippers, several generations
of designs were developed including
the following:
Titanium explosive-clad steel
equipment and solid Ti-3
tubes.
Various combinations of 2522-2 (Cr-Ni-Mo) stainless steel
(310MoLN) wetted internals
with zirconium lined / SS
(310MoLN) bimetallic tubes,
and with and without auxiliary
passivation air to protect the
(310MoLN) components.
Zircadyne explosive-clad
steel equipment and solid Zr
702 tubes.
OmegaBond tubes and
titanium-clad steel equipment.

In all the aforementioned corrosion

events with the 310MoLN stainless
steel, no deleterious effects were
observed to the zirconium material.
One example of the extreme
corrosion issue seen in the
310MoLN stainless steel weld
overlay between exchanger tubing
is seen in Figure 2. Such corrosion
caused leakage of process media
to the lower pressure side of the
exchanger and severe damage to
the carbon steel tube sheets.
In order to maintain production,
Profertil was required to undergo a
number of repairs to the original
commissioned unit. The severe
corrosion problems led Profertil to
repair and eventually plug over 500
of the 3600 tubes in the urea
stripper. Initially auxiliary passivation
air was not added to the lower
channel area to mitigate the
corrosion effects noted above.
However, when auxiliary passivation
air was added in 2002, the
corrosion attack continued. Efforts
to limit the lower channel operating
temperature to 204C (~400F)
were only partially successful in
lessening the corrosion attack in the
310MoLN stainless steel.
After input from other producers
operating facilities with a urea
stripper design similar to Profertils,

When the original commissioned

(2001) urea stripper design was
specified, the preferred wetted
internal materials of construction
were zirconium lined / SS
(310MoLN) bimetallic tubing and
stainless steel overlay (310MoLN
equivalent) on the channels. During
the initial operation of the urea
plant, Profertils urea stripper
experienced a number of corrosion
issues, largely confined to the
bottom (outlet) channel section.
These corrosion problems included
the following:
Corrosion in the 310MoLN
stainless steel tubesheet weld
overlay.
Corrosion in the 310MoLN
stainless steel weld overlay
applied to the lower channel
stainless steel lining.
Corrosion in the exposed
310MoLN stainless steel bimetallic tube ends and the
tube-to-tubesheet strength
welds.
Corrosion in the 310MoLN
tubes under the zirconium
tube (inner liner) caused by a
stagnant zone due to poor
bonding.

Zircadyne and OmegaBond are registered trademarks of ATI Properties, Inc.

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2C HIGH PRESSURE ZIRCONIUM UREA STRIPPER

and who in turn were suffering similar

corrosion behavior, the consensus
was Profertil had suffered some of
the worst corrosion effects based on
limited operating time. Additionally,
the view was that the 310MoLN
stainless steel was near its operating
temperature limits within the urea
stripper environment. Due to the on
going
corrosion
problems
experienced, Profertil began their
review of alternative materials of
construction.

MATERIAL EVALUATION &

SELECTION
Because of the extreme corrosive
conditions in the urea stripper, a
number of considerations had to be
taken into account to ensure that the
optimum material was selected. In
these severe conditions, the
corrosion resistance of the current
materials used was shown to be
dependent and very sensitive to
chemical variables of the process
conditions. Furthermore, it is wellknown that the corrosion resistance
behavior of these materials depends
strongly on using proper fabrication

practices. It has been reported a

number of times that strippers in the
same environment, manufactured
by different vendors, exhibit very
different behavior and performance.

even at 204C (400F). This

operating temperature limit is
exacerbated by slightly altered
material chemistry and properties
resulting from fabrication practices.
Thus small variations in the process
conditions, such as the NH 3 /CO 2
ratio (even for a short time of a few
hours), or an increased operating
temperature may lead to severe
corrosion of the materials. This high
sensitivity to the process conditions
reduces the plants flexibility and
increases the safety concerns for
operations. Even with adding the
passivation air it was thought that
the stainless steel was close to its
limit in regards to the corrosion
resistance.
The titanium design with the
clad liner plates and solid titanium
tubes was discounted as many urea
producers reported issues with
erosion / corrosion of the titanium
tubes in the upper section of the
heat exchanger. The corrosion /
erosion issue in the upper portion
of the heat exchanger resulted in
titanium urea stripper units to be
designed for rotation 180C (356F)
after approximately 810 years to
produce a cost effective production
usage.
Safurex had been considered
by Profertil but due to an exclusive
agreement between Sandvik and
Stamicarbon, the use of Safurex in
the Snamprogetti process was not
an option. Even though the Safurex
duplex stainless steel had proven
corrosion resistance over that of the
310MoLN stainless steels in the
Stamicarbon urea operations, the
corrosion resistance was less than
that expected for zirconium.
Following
a
one
year
investigation, Profertil selected the
option of fabricating the urea
stripper using zirconium lined steel
equipment with solid zirconium
tubes. The zirconium mill products
were obtained from ATI Wah Chang
and the fabrication of the vessel was
performed by Officine Luigi Resta,
SpA of Scanzorosciate, Italy [1] .

MATERIAL SOLUTIONS
CONSIDERED
Initially, a number of options were
investigated, but one option
discounted very quickly was to
fabricate another unit with the bimetallic tube design. The three
options considered were the
titanium design, the Safurex duplex
stainless steel design and the solid
Zircadyne zirconium tube design.
According to Proferils plant
experience, the 310MoLN stainless
steel bimetallic design may have
been used if the passive corrosion
state could be achieved but, as
experienced, slight changes in the
process conditions caused the SS
to revert to an active corrosion
state. It was understood that even
with passivation air addition into the
bottom of the stripper, the
310MoLN stainless steel was very
near its operating temperature limit,

Figure 2. Extreme corrosion seen in the 310MoLN weld overlay at the bottom tube
sheet between exchanger tubing.

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ZIRCONIUM
Zirconium had been used even in
the early 1960s in select chemical
applications by a small number of
chemical producers. At that time,
zirconium was primarily used in the
nuclear industry so very few
equipment manufacturers had ever
fabricated or welded reactive metals.
One of the first uses of zirconium for
the urea industry was in the urea
synthesis process where zirconium

zirconiums excellent resistance to

these severe environments. In
addition, fabrication techniques have
advanced to where very large solid
and explosive clad zirconium
columns, heat exchangers, reactor
vessels, piping systems, and
support equipment are readily
available for use in plants throughout
the world. Zirconium has excellent
corrosion resistance to many severe
environments including sulfuric acid,
nitric acid, hydrochloric acid, formic
acid, urea, and organics, in addition
to alkaline media.
A misconception is that
zirconium is an exotic and expensive
material and difficult to fabricate.
Zirconium equipment is very
competitive to the stainless alloys
and high-nickel alloys in regards to
life cycle costing.

had been in continual operation for

over 20 years with excellent
performance[2]. Zirconium has grown
to literally thousands of uses and is
able to be manufactured into
equipment and components by a
number of fabricators.
Over the past 40 years, the use
of zirconium has steadily increased
due to the development of chemical
processes requiring extremely
corrosion-resistant materials and

Table 1. Mechanical properties of zirconium alloys.

ZIRCONIUM MECHANICAL &

PHYSICAL PROPERTIES

Table 2. Chemical compositions of zirconium alloys.

Zirconium alloys for chemical

processing
applications
are
designated by three primary grades
for use in the chemical processing
industry (CPI). These three alloys (Zr
700, Zr 702 and Zr 705) are
commonly produced but only Zr 702
and Zr 705 are approved for use in
pressure containing vessels according
to the ASME Boiler and Pressure
Vessel Code. Tables 1 and 2 show the
mechanical and chemical properties
of these commercially available

Table 3. Physical properties of materials.

* 20-100C (70-212F), n.a = not available.

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zirconium alloys. Zr 702 has lower

strength and generally better
corrosion resistance than Zr 705. The
Zr 705 alloy, with 23% niobium, has
higher strength and better formability
than that of the Zr 702 grade. The Zr
700 grade is used for explosioncladding applications.
Zirconium is less dense than
stainless steel and has much better
thermal conductivity. Zirconium also
has a much higher melting point and
a very low thermal expansion as
compared to other materials used
in urea production facilities. Table 3
shows a comparison of properties
of materials used in urea production.

Figure 3. The completed vessel arriving at the Profertil fertilizer complex in Bahia
Blanca, Argentina.

CORROSION RESISTANCE
OF ZIRCONIUM
Zirconium has had a long history of
excellent
corrosion-resistant
properties in many applications.
There are a large number of
applications where zirconium has
been placed in extremely corrosive
environments for many years
without experiencing any corrosion
attack. In particular, zirconium
reactors and heat exchangers were
used in the urea services for over
25 years without showing signs of
corrosion attack. The primary use
of zirconium in the chemical
processing industry (CPI) has been
in organic acids (e.g., acetic acid
and formic acid) but also in mineral
acids such as nitric, sulfuric, and
hydrochloric acids.

titanium clad channels and heads

were used. It was found during the
fabrication of this zirconium urea
stripper that the conventional
reactive metals batten strap clad
construction methods were not
sufficient for this vessel [3] . After a
number of batten strap weld failures
during the construction process, it
was found that the new generation
of urea stripper would require
unique design and fabrication
techniques different from that used
in conventional construction
methods. Determining the proper
design required many weld tests
and stress analyses.
Officine Luigi Resta developed
a new technique based upon many
investigations and studies carried
out after hydrotest failures of the
original designed zirconium material
liners. The result is a new design of
the filler and cover straps based
upon a double filler strap and a
reduced thickness cover strap. With
this design, operating stress level is
lowered and peak stresses in the
area of the filler straps were
eliminated.
The incorporation of zirconium
as the corrosion-resistant material

equipment. Because zirconium is

ductile, it can be explosively-clad to
stainless or mild steel and fabricated
in clad vessels using the batten
strap technique. The earliest
zirconium vessel fabricated using
explosive-cladded material was in
the early 1970s. Since that time,
over 30 explosive clad pressure
vessels have been manufactured
with zirconium. Although zirconium
is a reactive metal, it can be readily
welded using equipment and similar
processes that are being used for
stainless steel equipment. Zirconium
is however, much more reactive
than stainless steel so greater
attention to cleanliness and
shielding is needed.

ZIRCONIUM FABRICABILITY
Zirconium has good fabricability. It
can be formed, machined, and
fabricated using conventional
techniques and equipment currently
applied to other more common
materials of construction. Zirconium
Grade 702 and Grade 705 are
currently approved for use in the
ASME Boiler and Pressure Vessel
Code. It is commonly fabricated into
solid and explosive-clad vessels for
use in chemical processing
C O R R O S I O N

ZIRCONIUM UREA STRIPPER

FABRICATION
Although zirconium had been used
in many heat exchanger designs
during the past 40 years, zirconium
had never been previously applied
as a solid tube material in a highpressure urea stripper. Officine Luigi
Resta had significant experience in
fabrication of previous urea strippers
where solid titanium tubing and

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Figure 4. The completed urea stripper awaiting installation at the Profertil fertilizer
complex in Bahia Blanca, Argentina.

Figure 5. The completed urea stripper

installation at Profertil, Bahia Blanca,
Argentina.

Figure 6. A thin crack located in the J-area during a routine internal inspection in
December 2008.

for the internal wetted surface of the

stripper provides the ultimate in
equipment lifetime and reliability.
Although more costly up front than
the 310MoLN stainless steel option,
the corrosion rate of zirconium is
known to be essentially nil in the
urea process environment, leading
to an equipment life that is projected
to exceed the rest of the plant. Since
the completion of the Profertil
zirconium stripper, ATI Wah Chang
has introduced OmegaBond tubing,
a further refinement to the
equipment design.
C O R R O S I O N

the zirconium components.

Only one very thin crack was
found in the J-area between tube
sheet to channel barrel section
(Figure 6), which was repaired by
Officine Luigi Resta field service. The
reason for this crack has not been
confirmed, and the depth of the
crack was very minor in length.
The stripper is operated with
an outlet temperature of 210C
(410F) for testing and for
observations on whether this higher
operating temperature will impact
positively in downstream medium
and lower pressure sections. In the
previous bimetallic urea stripper the
outlet temperature had been limited
to 204C (400F) for corrosion
issues placing higher loads on the
down stream medium and lower
pressure sections.
Profertil S.A. is currently
studying this as urea plant capacity
increases and the stripper is not
considered a bottleneck to such a

OPERATION EXPERIENCE
The final constructed zirconium urea
stripper was placed in service in
January 2007. Figures 3, 4, and 5
show photographs of the vessel
arriving at site, waiting for installation,
and in the final stages of installation
into the urea plant, respectively.
In December 2008, during a
scheduled turn around, an
inspection was carried out in the
stripper (tube sheets, tubes, lining
system, other internals, etc.). The
results of this investigation showed
no evidence of corrosion on any of

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capacity increase.
Profertils expectations are that
the zirconium urea stripper will
outlive the remaining life of the rest
of the urea plant equipment.

CONCLUSION

as compared to the other materials

considered.
The advanced design developed
by Officine Luigi Resta enabled
zirconium solid tubes and clad shell
to be built into this new generation
urea stripper. a

2.

3.

The use of zirconium in the design

of this urea stripper was shown to
be the most reliable option for
Profertils urea plant.
The use of zirconium was also
found to be the lowest life cycle cost

C O R R O S I O N

REFERENCES
1.

Jorge Versace, New Urea

High-Pressure Zr Stripper
Development, Profertil S.A.
Argentina, Snamprogetti

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licensees meeting, 2001.

Zirconium Outlives Urea
Synthesis Technology for
which it was Designed,
Outlook, Vol. 7, No. 1,
Teledyne Wah Chang, Albany,
OR, 1986.
P. Mantovani, Improved
Lining Technique in HighPressure Urea Stripper Lined
with Reactive Metals, Officine
Luigi Resta, Corrosion
Solutions Conference 2009,
Park City, UT, 2009.

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