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— P A P E R 2 C
High-Pressure Zirconium
Urea Stripper
GUILLERMO BARTELLI ABSTRACT
PRODUCTION SUPERINTENDENT Profertil, an Argentine company
Profertil S.A. Argentina equally owned by Agrium Inc. and
Puerto Ingeniero White Repsol-YPF S.A., is located in
Zona Cangrejales Ingeniero White, Bahía Blanca,
B8103 Bahia Blanca, Buenos Aires Argentina. This plant has a name
Argentina plate production capacity of 2050
T: 54 29 1453 3527 mt/day of ammonia and 3250
E: gbaratel@profertil.com.ar mt/day of urea and was
commissioned in January 2001. The
ammonia plant is a Haldor Topsoe
Co-authors design; the urea plant is a
Snamprogetti design (now known as
PIETRO MANTOVANI Saipem SpA). The production plant
Officine Luigi Resta SpA represented the largest design
capacity for any single train
GIANPIETRO TESTA ammonia or urea plant operating in
Saipem SpA the world at that time. Maximum
production achieved has been 2278
DON TIMBRES mt/day for ammonia (~12% above
D&E Consulting Inc. name plate design) and 3719 mt/day
for urea (~14% above name plate
RICHARD SUTHERLIN, PE design). Figure 1 shows an aerial
ATI Wah Chang view of the Profertil fertilizer complex
in Bahia Blanca, Argentina.
B.J. SANDERS Within the first year of start-up,
B.J. Sanders and Associates Inc. Profertil suffered severe corrosion to
the stainless steel alloy wetted
JORGE VERSACE internals (310MoLN – UNS S31050
Profertil S.A. Argentina – also known as 25-22-2 Stainless
Steel) of a critical vessel (the urea
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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 zirconium-
lined equipment and solid zirconium
tubes for this urea stripper entailed
significant research and a non-
conventional design. This paper will
review the process used in selecting
zirconium, developing a specific heat
exchanger design and fabrication of
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72 2C — HIGH PRESSURE ZIRCONIUM UREA STRIPPER

this urea stripper. This paper will also Figure 1. Aerial view of the Profertil fertilizer complex.
review the operating experience and
success achieved after nearly three
years in service.

KEYWORDS
• zirconium
• urea production
• urea stripper
• Omegabond ®
• Zircadyne ®
• stainless steel
• organic acids
• mineral acids
• ammonia
• heat exchanger
• chemical process industry
• UNS S31050 INITIAL CORROSION In all the aforementioned corrosion
PROBLEMS events with the 310MoLN stainless
INTRODUCTION When the original commissioned steel, no deleterious effects were
The high-pressure urea stripper (2001) urea stripper design was observed to the zirconium material.
exists in one of the most severe specified, the preferred wetted One example of the extreme
process conditions in the urea plant. internal materials of construction corrosion issue seen in the
The urea stripper is a vertical heat were zirconium lined / SS 310MoLN stainless steel weld
exchanger (falling film evaporator) (310MoLN) bimetallic tubing and overlay between exchanger tubing
which operates under high stainless steel overlay (310MoLN is seen in Figure 2. Such corrosion
temperatures and pressures. equivalent) on the channels. During caused leakage of process media
Historically, a number of material the initial operation of the urea to the lower pressure side of the
solutions have been applied to the plant, Profertil’s urea stripper exchanger and severe damage to
Snamprogetti (Saipem SpA) urea experienced a number of corrosion the carbon steel tube sheets.
stripper design. Because of the issues, largely confined to the In order to maintain production,
severe corrosion experiences with bottom (outlet) channel section. Profertil was required to undergo a
urea strippers, several generations These corrosion problems included number of repairs to the original
of designs were developed including the following: commissioned unit. The severe
the following: corrosion problems led Profertil to
• Corrosion in the 310MoLN repair and eventually plug over 500
• Titanium explosive-clad steel stainless steel tubesheet weld of the 3600 tubes in the urea
equipment and solid Ti-3 overlay. stripper. Initially auxiliary passivation
tubes. • Corrosion in the 310MoLN air was not added to the lower
• Various combinations of 25- stainless steel weld overlay channel area to mitigate the
22-2 (Cr-Ni-Mo) stainless steel applied to the lower channel corrosion effects noted above.
(310MoLN) wetted internals stainless steel lining. However, when auxiliary passivation
with zirconium lined / SS • Corrosion in the exposed air was added in 2002, the
(310MoLN) bimetallic tubes, 310MoLN stainless steel bi- corrosion attack continued. Efforts
and with and without auxiliary metallic tube ends and the to limit the lower channel operating
passivation air to protect the tube-to-tubesheet strength temperature to 204°C (~400°F)
(310MoLN) components. welds. were only partially successful in
• Zircadyne ® explosive-clad • Corrosion in the 310MoLN lessening the corrosion attack in the
steel equipment and solid Zr tubes under the zirconium 310MoLN stainless steel.
702 tubes. tube (inner liner) caused by a After input from other producers
• OmegaBond ® tubes and stagnant zone due to poor operating facilities with a urea
titanium-clad steel equipment. bonding. stripper design similar to Profertil’s,

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

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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 well-
known that the corrosion resistance
behavior of these materials depends
strongly on using proper fabrication
Figure 2. Extreme corrosion seen in the 310MoLN weld overlay at the bottom tube
sheet between exchanger tubing.
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2C — HIGH PRESSURE ZIRCONIUM UREA STRIPPER
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.
MATERIAL SOLUTIONS
CONSIDERED
Initially, a number of options were
investigated, but one option
discounted very quickly was to
fabricate another unit with the bi-
metallic 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 Proferil’s 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,
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even at 204°C (400°F). 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 plant’s 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 180°C (356°F)
after approximately 8–10 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] .
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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
Table 1. Mechanical properties of zirconium alloys.
Table 2. Chemical compositions of zirconium alloys.
Table 3. Physical properties of materials.
* 20-100˚C (70-212˚F), n.a = not available.
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2C — HIGH PRESSURE ZIRCONIUM UREA STRIPPER
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
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zirconium’s 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.
ZIRCONIUM MECHANICAL &
PHYSICAL PROPERTIES
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
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zirconium alloys. Zr 702 has lower
strength and generally better
corrosion resistance than Zr 705. The
Zr 705 alloy, with 2–3% niobium, has
higher strength and better formability
than that of the Zr 702 grade. The Zr
700 grade is used for explosion-
cladding 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.
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.
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
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2C — HIGH PRESSURE ZIRCONIUM UREA STRIPPER
Figure 3. The completed vessel arriving at the Profertil fertilizer complex in Bahia
Blanca, Argentina.
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 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 high-
pressure urea stripper. Officine Luigi
Resta had significant experience in
fabrication of previous urea strippers
where solid titanium tubing and
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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
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Figure 4. The completed urea stripper awaiting installation at the Profertil fertilizer
complex in 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.
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2C — HIGH PRESSURE ZIRCONIUM UREA STRIPPER
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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Figure 5. The completed urea stripper
installation at Profertil, Bahia Blanca,
Argentina.
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 210°C
(410°F) 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 204°C (400°F) 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
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capacity increase.
Profertil’s expectations are that
the zirconium urea stripper will
outlive the remaining life of the rest
of the urea plant equipment.
CONCLUSION
The use of zirconium in the design
of this urea stripper was shown to
be the most reliable option for
Profertil’s urea plant.
The use of zirconium was also
found to be the lowest life cycle cost
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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
REFERENCES
1. Jorge Versace, “New Urea
High-Pressure Zr Stripper
Development,” Profertil S.A.
Argentina, Snamprogetti
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licensees meeting, 2001.
2. “Zirconium Outlives Urea
Synthesis Technology for
which it was Designed,”
Outlook, Vol. 7, No. 1,
Teledyne Wah Chang, Albany,
OR, 1986.
3. P. Mantovani, “Improved
Lining Technique in High-
Pressure Urea Stripper Lined
with Reactive Metals,” Officine
Luigi Resta, Corrosion
Solutions Conference 2009,
Park City, UT, 2009.
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