Duplex Stainless Steels 97 - 5th World Conference

D97-201
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Application of duplex stainless steel in the chemical

process industry

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by Giel Notten (DSM Engineering Stamicarbon, the Netherlands)

Keywords: duplex stainless steel, chemical process industry, stress corrosion cracking, selective attack, urea

Abstract
The use of duplex stainless steels in the
chemical process industry has expanded
rapidly over the past few years. They are
now used not only in chloride environments, where they are more resistant to
SCC than austenitic stainless steels, but
also in a wide variety of other demanding
applications.
In DSM plants, duplex is used especially
for chloride-containing process fluids
and for ammonium carbamate solutions.
The material has been found to offer
good resistance to chloride SCC, although such corrosion can and does occur at pH values lower than 3 to 4. This
we established both in the field and
through CERT (constant extension rate
testing).
In a strongly alkaline chloride-bearing solution, duplex SS gives excellent performance whilst a high-nickel alloy fails after
about three years because of SCC. These
findings are supported by drop evaporation tests.
In oxygen-free carbamate solutions, duplex has proved to be even more corrosion resistant than much more costly materials such as titanium and high-nickel
alloys. In the high-pressure synthesis
section of urea plants, duplex is an excellent alternative to traditional urea grades
such as type AISI 316 L UG and
X2CrNiMoN 25 22 2. These are particularly prone to SCC on the steam side of heat
exchangers when the boiler feedwater is
contaminated with chlorides.
Fabrication of high-pressure vessels in
duplex is not without difficulty, however.
Also, the duplex must meet particular
quality requirements to ensure proper
performance in carbamate environments.
These have meanwhile been defined in a
DSM/Stamicarbon material standard.
Use of duplex SS can offer significant
cost savings. As a case in point, a condenser, which has given 12 years of satisfactory service, cost US $ 300,000. The
same vessel in high-nickel alloy would
have cost US $ 1,000,000.

Duplex SS, because of its higher strength

figures, offers a 10% cost saving over
austenitics in the high-pressure piping
used in the urea synthesis section.
Sandvik, in collaboration with
Stamicarbon, the licensing subsidiary of
DSM, has developed a new type of duplex SS. Named Safurex, this material offers optimum corrosion resistance to
carbamate environments.

1 Introduction
At DSM, duplex stainless steels were first
applied in the mid-nineteen sixties, mainly
for non-welded parts of carbamate pumps
and valves in urea plants. In the late nineteen sixties, the drum of a centrifuge in a
polyethylene plant was fabricated from
X2CrNiMoCu 21 8 3 2 to replace a type AISI
316 drum exhibiting serious chloride stress
corrosion cracking. Large-scale introduction
of duplexes began in the early eighties, initially for piping and equipment components
and later for large-size equipment. At the
present time, some US $ 60 million worth of
duplex is used in DSM plants.
They are used on services such as the following:
oxygen-free carbamate solutions at temperatures up to about 130C, replacing titanium and high-nickel alloys;
oxygen-containing carbamate solutions
at temperatures up to about 185C;
benzoic acid at temperatures of 240C to
260C, where previously high-nickel alloys were used;
chloride-containing solutions where the
typical austenitic stainless steels are susceptible to stress corrosion cracking
and/or corrosion fatigue;
caustic fluids at temperatures up to
200C;
calcium ammonium nitrate and NPK fertiliser;
nitric acid and acidic ammonium nitrate
solutions.

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Contents

Authors
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Application of duplex stainless steel in the chemical process industry

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Various types of duplexes have been used

here including 22% Cr and 25% Cr grades
like X2CrNiMoN 22 5 3 and X2CrNiMoCuN
25 7 3 2. For nitric acid and acidic ammonium nitrate solutions the molybdenum-free
type X2CrNiN 23 4 is used. The workhorse
among the duplexes used in DSM and
Stamicarbon-licensed plants is X2CrNiMoN
22 5 3. This gives good performance in, for
example, a 12% NaCl solution with pH 14 at
temperatures up to 200C. In one instance it
has lasted for nine years without any failure
while a high nickel alloy failed after 2 years
due to stress corrosion cracking.
Laboratory stress corrosion cracking examinations by means of drop evaporation tests
(DET) showed that duplex stainless steels
have a better stress corrosion cracking resistance in alkaline (chloride containing) solutions than high-nickel alloys.
Experience with duplex stainless steels in
oxygen-free carbamate solutions was first
reported at the 9th European Congress on
Corrosion, 26 October 1989 in Utrecht, the
Netherlands (ref. 1). The first large-scale application of duplex stainless steel on this
service was a condenser which gave 12
years of satisfactory service. The same unit
in titanium and a high-nickel alloy had to be
replaced after 5 and 8 years respectively.
The duplex cost US $ 300,000 while at the
time a high-nickel alloy unit would have cost
US $ 1,000,000.
This paper discusses the application and
benefits of duplexes used on urea service. It
also reports on a new duplex stainless steel
specially developed for carbamate service
in urea plants.

2 Stamicarbon CO2-stripping urea

process
(Ref. 2) The production of urea is based on
the following reaction mechanism:
2 NH3 + CO2

NH2COONH4

NH2COONH4

CO(NH2)2 + H2O

The process flow diagram of the

Stamicarbon stripping process is shown in
figure 1. The synthesis section consists of a
urea reactor (c), a stripper for unconverted
reactants (d), a high-pressure carbamate
condenser (e) and a high-pressure off-gas
scrubber (f). In the carbamate condenser (e)
CO2 and NH3 are converted into ammonium
carbamate. In the reactor the ammonium
carbamate is partly converted into urea and
water.
The urea synthesis process takes place at a
pressure of 140 bar and a temperature of
185C. The bulk of the unconverted carbamate decomposes in the stripper, where
ammonia and carbon dioxide are stripped
off. This stripping is effected by countercurrent contact between the urea solution
and oxygen-containing carbon dioxide at
synthesis pressure. The oxygen is needed
to maintain a passive (corrosion resistant)
layer on the stainless steels in the synthesis
section. On leaving the stripper, gaseous
ammonia and carbon dioxide are condensed in the high-pressure carbamate
condenser (e) at synthesis pressure. Before
being purged from the synthesis section,
the inert gases, mainly oxygen and nitrogen,
are washed in the high-pressure scrubber (f)

Figure 1. Stamicarbon CO2- stripping urea proces.

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with carbamate solution from the low-pressure recirculation section.

The urea synthesis solution is highly corrosive, the most aggressive component being
ammonium carbamate. Consequently, materials of construction to be used here must
meet high standards in terms of composition and quality. Awareness of the important
factors in materials selection, equipment
design, manufacture and inspection, technological design and proper plant operations, together with periodic corrosion inspections, are the key factors for safe
operation for many years.

3 Corrosion aspects
3.1 Condensation corrosion
Stainless steels in a corrosive environment
like ammonium carbamate owe their corrosion resistance to the presence of a protective oxide layer on the surface. As long as
this layer is intact, the metal corrodes only
at a very low rate. Passive corrosion rates in
liquid phases are generally between 0.01
and 0.1mm/year. In gas phases where mixtures of ammonia, carbon dioxide and water
vapour can condense to form carbamate
solutions passive corrosion rates can increase to 0.2mm/year. Active corrosion
rates in carbamate solutions can be as high
as 50mm/year. Stainless steels exposed to
carbamate-containing solutions in urea synthesis section can be kept in a passivated
state by adding a given amount of oxygen.
If the oxygen content drops below this limit,
acive corrosion starts after some time.
Adding oxygen and maintaining a sufficiently high oxygen content in the various
process streams are prerequisites to preventing corrosion of the equipment and
pipelines.
From the point of view of corrosion prevention, condensation of NH3-CO2-H2O gas
mixtures to carbamate solutions warrants
extra attention. Despite the presence of
oxygen, a more corrosive condensate is initially formed on condensation. Passivation
is believed to take place via a metal ion redox system, which is missing in freshly
formed condensate. This accounts for the
severe corrosion sometimes observed in
cold spots in the channels of HP equipment
and gas lines fabricated from urea grade
316L. Such corrosion can be prevented by
adequate insulation and tracing.
When condensation forms part of the
process, as in the HP carbamate condenser,

special technological measures must be

taken. One such measure is adding an oxygen-rich liquid phase containing a metal ion
redox system into the condenser, with liquid-gas distribution devices preventing dry
spots on surfaces where condensation
takes place.
The risk of condensation corrosion can also
be diminished by choosing a more corrosion-resistant material of construction. The
higher alloyed austenitic stainless steel type
X2CrNiMoN 25 22 2 is less susceptible to
condensation corrosion than urea grade
316L. Type X2CrNiMoN 22 5 3 duplex stainless steel has proved to be more corrosionresistant in condensing environments too.
Another benefit of duplex stainless steels is
their higher strength. Duplex high-pressure
piping can be much thinner than austenitic
stainless steel piping.
During a turnaround in October 1996, after
being on-stream for about 28 years, the
strip gas line from the HP stripper (d) to the
HP carbamate condenser (e) had to be replaced due to condensation corrosion. The
urea grade 316L line, measuring 219 X
22.2mm and 70 m long had a corrosion allowance of about 6mm. For duplex stainless
steel a corrosion allowance of 4mm will do,
so leading to 219 X 14mm pipe.
Replacement by type X2CrNiMoN 22 5 3
duplex (seamless hot extruded) pipe gave a
cost saving of about 10%.
Another advantage of duplex is its high resistance to chloride stress corrosion cracking. This can be particularly relevant for
plants in coastal areas. Such piping in austenitic stainless steel needs to be suitably
painted to minimise the risk of SCC. Duplex
stainless steel piping need not be painted.
3.2

Stress corrosion cracking in HP carbamate

condenser
The ammonia and carbon dioxide leaving
the stripper are condensed in the HP carbamate condenser (e) at synthesis pressure.
The heat released in the formation of ammonium carbamate is used for the production of 4.5 bar steam. Any chlorides entering
the shell side of the HP carbamate condenser are likely to initiate stress corrosion
cracking of the austenitic stainless steel
tubes, starting from the outside surface of
the tubes. Numerous cases of stress corrosion cracking are on record. Cracking has
been observed in both urea grade 316L and
X2CrNiMoN 25 22 2 tubes. An example of
stress corrosion cracking a urea grade AISI
316L HP carbamate condenser tube is

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Application of duplex stainless steel in the chemical process industry

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Figure 3. The location of cracks in HP carbamate condenser tubes.

Figure 2. External stress corrosion cracking of urea

grade AISI 316L HP carbamate condenser tube ( 25 X
20mm). Magn. 30; etchant oxalic acid; neg. nr.
7/83682-24.

shown in figure 2. The location of the cracks

is indicated in figure 3 for expanded-andwelded tubes and for welded tubes.
Stamicarbon does not allow the tubes to be
expanded in the tubesheet because this
would render the leak detection system inoperative.
Leakage may result from pinholes in the
tube joints. In most cases cracking merely
occurred in or near the top tubesheet. The

Figure 4. Steam and condensate system in the urea process.

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locations have been found to depend on the

origin of the chloride contamination.
The following causes of SCC in HP carbamate condensers have been identified:
Chloride contamination of water used for
hydrostatic testing, cleaning or flushing.
Transport and storage in a chloride-containing (maritime) atmosphere (infiltration
as a result of breathing due to cyclic
temperature changes).
Chloride contamination of boiler feed water (e.g. leakage of vent condenser in
steam condensate tank). The steam and
condensate system in the urea process is
shown in figure 4.
SCC in HP carbamate condensers can be
avoided by changing the corrosive environment (inhibition) or by using a material that
is more resistant to chloride SCC:
The chloride content of water used for
hydrostatic testing, flushing or cleaning
should be less than 1 ppm. As an additional precaution it is advised to inhibit
the water with 2% TSP (trisodium phosphate).
During transport and storage in a chloride-containing atmosphere the equipment should be inerted with nitrogen
(0.3-0.5 bar gauge).
The chloride content of the blow-down
should be less than 0.2 ppm. The oxygen
content should be zero; this will be the
case when the blow-down contains excess oxygen scavenger (0.10.5 ppm). If
chloride contamination cannot be avoided, continuous inhibition with TSP should
be considered.
Application of a more SCC-resistant material like type X2CrNiMoN 22 5 3 duplex
stainless steel.
For existing carbamate condensers the
remedies were focused on changing the environment but for new equipment the use of
duplex stainless steel was considered. We
had gained ample experience with such
steels in terms of SCC resistance.
In a naphtha cracking plant of DSM two
process steam generators, with U-bundles
in type X2CrNiMoN 22 5 3 duplex stainless
steel, have been in service since 1988.
Conditions on the shell side are even more
severe than in carbamate condensers.
Steam is generated from chloride-containing process condensate (average chloride
content 10 ppm with pH varying from 412)

at a temperature of 180C. The carbon steel

tubesheet is overlay welded with AISI 309L
(X2CrNi 24 12). The duplex stainless steel
tubes were automatically welded (GTAW)
with 309S/309Mo welding consumable. The
tubes were lightly expanded within the
tubesheet over a length of 25mm. The thickness of the tubesheet is 193mm. A light hydraulic expansion cannot prevent crevices
between the tubes and the tubesheet. The
horizontal bundle is not fully immersed, accumulation of corrosive components like
chlorides is likely to occur in the wet/dry
zone. Until now, after about nine years on
stream, no corrosion has been observed in
these steam generators. In numerous other
applications we found that duplex stainless
steels offer good SCC-resistance at pH values above about 4. At lower pH values the
advantage of duplex stainless steels over
austenitic stainless steel diminishes. This
has been confirmed in stress corrosion
cracking experiments by means of Constant
Extension Rate Testing (CERT) (ref. 1, 3).
Duplex stainless steel test coupons have
been exposed in the HP synthesis section
of the DSM urea plant since the mid-seventies. The average corrosion rate of
X2CrNiMoN 22 5 3 proved to be as follows:
top of reactor: 0.04mm/year
top of stripper: 0.08mm/year
top of HP carbamate condenser:
0.03mm/year
The corrosion rates of duplex stainless steel
in the urea reactor and in the HP carbamate
condenser are comparable with those of
X2CrNiMoN 25 22 2. The measured corrosion rate of duplex in the stripper is slightly
higher than that of type X2CrNiMoN 25 22 2
steel. Based on these results and experience with chloride-containing environments,
we wondered if the chloride stress corrosion
cracking problems in the HP carbamate
condenser could be resolved by using duplex stainless steel instead of urea grade
316L or X2CrNiMoN 25 22 2.
In order to assess the corrosion resistance
of duplex stainless steel, we installed three
tubes of X2CrNiMoN 22 5 3 in the HP carbamate condenser of the DSM urea plant
for a period of 1.5 years. After this period, a
maximum decrease in wall thickness of
0.05mm was found. Corrosion was slightly
intergranular and had propagated via the
ferrite/austenite grain boundaries (figure 5).
In October 1993, the first HP carbamate
condenser and HP scrubber with

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Figure 5. Slight intergranular attack in duplex stainless

steel tube material exposed in HP carbamate condenser. Magn. 700; etchant KOH. Neg.nr. 7/82850.

Figure 6. Part of seriously corroded stripper tube

( 3125mm) due to flooding. Neg. nr. 7/83861-32.

duplex stainless steel tubes and tubesheets

overlay welded with duplex stainless steel
were installed in a urea plant. In September
1996, after 3 years on stream, the HP heat
exchangers were checked by visual inspection and eddy current measurements of the
tubes.
This inspection revealed no signs of corrosion, neither of the overlay welding and
tube-to-tubesheet joints, nor of the tubes.
A HP carbamate condenser with duplex
stainless steel tubes and overlay welded
tubesheets is only slightly more expensive
than the same unit in urea grade AISI 316L
and about 5% cheaper than one in
X2CrNiMoN 25 22 2.
Three other HP heat exchangers with duplex stainless steel tubes and overlay welded tubesheets are now under construction.
3.3 Corrosion of HP stripper tubes
In the stripper the unconverted carbamate is
decomposed and the ammonia and carbon
dioxide are stripped off. Stripping is effected
by countercurrent contact between the urea
solution and carbon dioxide at synthesis
pressure. The stripper is the falling film type.
Liquid dividers with gas tubes are positioned on the protruding tube ends with the
joints being sealed with PTFE bushes.
Process conditions are severest in the stripper, especially at the top of the tubes, due
to the relatively low oxygen partial pressure
and high tubewall temperature. In the
Stamicarbon urea stripping plants the stripper tubes are fabricated from X2CrNiMoN
25 22 2. The corrosion rate of this material
in these conditions is 0.05mm/year, which is
quite low. If a liquid divider with PTFE bush
is not properly seated a higher corrosion
rate may occur due to flooding in the tube.
Figure 6 shows part of a seriously corroded
stripper tube due to flooding.
Given the performance of duplex stainless
steels in oxygen-containing and oxygen-free
carbamate solutions we feel sure that a duplex high in chromium and nitrogen and low
in nickel will give good performance even in
these extreme conditions.

4 Material requirements for duplex

stainless steels
Figure 7. Intergranular attack of type X2CrNiMoN 22 5
3 duplex in Streicher test. Magn. 140; etchant LB1;
neg. nr. 76350.

Experience has shown that duplex stainless

steels to be exposed to carbamate solutions
must meet particular requirements. They
must have a homogeneous ferrite-austenite
structure consisting of a ferritic matrix with
austenite islands fully enclosed by ferrite.

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The ferrite content of the base material must

be between 40 and 60% whilst the ferrite
content of the weld and the heat-affected
zones must be between 30 and 70%. A lot
of effort has been put into the development
of a suitable quality test. We found that the
Streicher test (ASTM A 262, Practice B) fills
the bill. Duplex stainless steel test coupons
that showed intergranular attack on exposure to carbamate solutions showed also intergranular attack in the Streicher test (figure
7).
We therefore decided that duplex stainless
steels on ammonium carbamate service
should be Streicher-tested in accordance
with ASTM A 262 Practice B. Such steels
shall meet the following requirements:
The value of the overall attack in as-delivered and in the final heat-treated condition
(e.g. welding) as determined by the gravimetric method shall not exceed:
1.6 g/m2 h. (10 m/48 hr) for 22% Cr duplex types;
0.9 g/m2 h. (6 m/48 hr) for 25% Cr duplex types.
The depth of selective or intergranular attack as determined by microscopic examination after the Streicher test shall not exceed 100 m in any direction.
Heat exchanger tubes shall be tested for
homogeneity (ferrite-austenite ratio) by
eddy-current testing. Longitudinally welded
heat exchanger tubes are not acceptable.
These requirements are included in the
Stamicarbon material specification.

5 Development of a new type of duplex

stainless steel for ammonium carbamate service
Sandvik and Stamicarbon decided to jointly
develop a new type of duplex stainless steel
specifically for urea synthesis equipment
and piping (ref. 4), This new type of duplex,
named Safurex, was to have the following
properties:
At least the same corrosion resistance to
carbamate solutions as X2CrNiMoN 25
22 2.
High resistance to stress corrosion cracking.
Superior mechanical properties to urea
grade AISI 316L and X2CrNiMoN 25 22 2.
Good microstructure stability.
Good weldability.

For exploratory tests, Sandvik produced

several heats with different chemical compositions in a 170 kg ingot HF laboratory
furnace. From the test results, laboratory
examinations as well as field tests of some
twenty heats with different chemical compositions the optimum alloy composition with
respect to corrosion resistance, structure
stability and weldability was selected. This
composition is used in SafurexTM. It contains in % by weight:
C
max. 0.05
Si
max. 0.8
Mn 0.34
Cr 28-35
Ni 310
Mo 1.03.0
N
0.20.6
Cu max. 1.0
W
max. 2.0
S
max. 0.010
Ce 00.2
the balance being Fe.
For a follow-up research programme a 70tonne AOD (argon oxygen decarburisation)
production heat of SafurexTM was made.
The investigations in laboratory experiments
and field tests gave the following results:
Safurex meets the following requirements
in the Streicher test to ASTM A 262,
Practice B:
overall attack:
< 0.7 g/m2/h
(0.78mm/year)
selective attack: < 100 m.
Safurexs corrosion resistance to carbamate solutions is equal to or better than
that of type X2CrNiMoN 25 22 2 material.
The stress corrosion cracking resistance
of Safurex is much better than that of
austenitic stainless steels and equal to or
even better than that of type X2CrNiMoN
22 5 3.
The tensile strength of Safurex is about
twice as high as that of urea grade AISI
316L and about 70% higher than that of
X2CrNiMoN 25 22 2.
The elongation of Safurex is >25% (A5).
Safurex has a homogeneous microstructure with a ferritic matrix which fully encloses the austenite islands.
Annealing and welding tests have shown
good microstructure stability.
Welding tests by GTAW using a matching
Safurex filler wire and a matching

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X2CrNiMoN 25 22 2 filler wire have

shown good weldability.
Like all duplex stainless steels, Safurex is
susceptible to 475C embrittlement.
However, a holding time of 10 hours at
510C does not cause any loss of ductility.

6 Conclusions
Given their excellent corrosion resistance, higher strength and lower cost duplex stainless steels are an attractive alternative to austenitic stainless steel HP
piping in urea plants.
For plants in coastal areas duplex stainless steel has the added advantage of
high chloride stress corrosion cracking
resistance.
Duplex stainless steels offer a good solution to stress corrosion cracking problems in the HP carbamate condensers.
Such cracking can be initiated by chloride contamination of the condensate.
SafurexTM, is a promising material that
withstands the severest corrosive (-erosive) conditions in carbamate solutions

combined with a high strength and good

stress corrosion cracking resistance.
References
1 Experiences with ferritic-austenitic stainless steels
in the chemical process industry. M.J.G. Notten,
DSM Stamicarbon, Geleen, The Netherlands.
Proceedings PI-038; 9th European Congress on
Corrosion. 26 October 1989, Utrecht, the
Netherlands.
2 Ullmans Encyclopedia of industrial chemistry; Urea;
Vol. A 27. Jozef H. Meessen, DSM Stamicarbon,
Geleen, the Netherlands. Harro Petersen, BASF
Aktiengesellschaft (retired), Ludwigshafen, Federal
Republic of Germany.
3 Stress corrosion cracking of duplex stainless steel
in chloride containing media in the chemical
process industry; a case study. J.G.A. Aerts and
M.J.G. Notten, DSM Stamicarbon, Geleen, the
Netherlands. Proceedings Duplex Stainless Steels
91, page 11411146. 2830 October 1991,
Beaune, Bourgogne, France.
4 Safurex, a new stainless steel for urea service. Giel
Notten and Jo Eijkenboom, DSM Stamicarbon,
Geleen, the Netherlands. Pasi Kangas and Ad
Raatgeep, Sandvik, Sandviken, Sweden. Eighth
Stamicarbon Urea Symposium 69 May 1996,
Amsterdam.

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