High temperature Nitriding

corrosion in
Ammonia converters
This paper provides case histories of failures in ammonia converters and their exchangers, different failures
occurred in tubes, tubesheets, basket, thermowell and thermal barrier, two failed samples were as brittle as a
glass. Investigation on samples which were in services between 3 -25 years, showed that the main reason of
failures was Nitridation due to presence of high pressure, high temperature and nitrogen environment.

By increasing the Nickel content in the steel, the Nitriding rate decrease but doesn't stop. By the way, the
Nitrated layer increased as the plant aged, subsequently ductility decreased sharply.

A. Hassan Faraji
Razi Petrochemical Co.-Iran

Introduction

R azi Petrochemical Complex (RPC) is one
of the largest fertilizer plant in Iran
was formerly a Subsidiary of National
Petrochemical Company (NPC), it is located on
the northern coast of the Persian Gulf. RPC was
privatized in February 2008 and a consortium of
Turkish companies acquired RPC in an
international tender. New shareholders are Gubre
Fabrikalari Turk Anonim sirketi – Asya gas
energy – Tabosan -Shghayegh Sazeh Rangin and
personnel.
The plant was commissioned in 1969. Design
capacity is 3.4 MMTPY (Million Metric Ton Per
Day) produces ammonia, prill and granular urea,
granular sulphur, Phosphoric and sulphuric acids
and D.A.P.
The complex comprise of three gas treating units,
three sulfur recovery units, two sulfuric plants, a
phosphoric plant, two D.A.P. plants, a urea plant
and three ammonia plants.
The ammonia plants were designed by M.W.
Kellogg and Ammonia Casale and commissioned
in 1969, 1975 and 2008 respectively. The
complex was out of service during Iran –Iraq war
activities for 8 years (1980-1988).
Discussion
This paper discusses eight case studies of
Nitriding attack that have occurred with stainless
steel in converters of Ammonia plants over long
periods.

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 High temperature corrosion:

Most popular modes of high temperature

corrosion are: Oxidation – Carburization –Metal
dusting –Sulfidation –Nitridation. The process of
high temperature normally comes with high
pressure as well. Carburization and Nitridation are
similar but they are different to other modes of
high temperature corrosion.

Nitriding

The Nitriding process was found about a century

ago. This process is used for improving
mechanical properties (for instance case
hardening) of low alloy steels at high temperature
(about 932 °F/500°C) by presence of ammonia
environment.
Nitriding is a chemical process that results from
diffusion of Nitrogen into the metal. When the
concentration of nitrogen exceeds solubility limit,
precipitation of nitrate in the metal occurs in the
matrix as well as at grain boundaries.
Based on equilibrium phase diagram of Nitrogen-
Iron (Fig. 1) because of partial solubility of
Nitrogen in Iron (up to 6%), gamma prime (γ’)
with composition of Fe4N is formed. The Gamma
prime layer is very hard and brittle (white layer).
The external layer is consisting of Gamma- Fe2-
3N, Gamma prime (γ’- Fe4N) and Chromium
Nitrate (CrN). Two types of Chromium Nitrates
were formed which were in the external layer
(CrN) and in internal layer (Cr2N).
When Nitrogen content in the steel is more than
8%, Epsilon compound (Fe3N) is formed (Fig. 1).
The Nitrided layer causes the austenitic stainless
steel to be magnetic.
Figure 1- Iron- Nitrogen equilibrium diagram
Nitriding mechanism
This phenomena consists of:
• Adsorption of ammonia in the metal surface.
• Ammonia decomposition to Nitrogen and
Hydrogen.
• Diffusion of N into the steel then formation
of FeN, Fe3N, Fe4N (in steel).
• Diffusion of N into the stainless steel then
formation of CrN, Cr2N, FeN, Fe3N, Fe4N (in
stainless steel).
If Carbon/Carbon compound exists the Nitriding
rate increases.
There are two parameters that influence
Nitriding:
• Process parameters (Temperature-Ammonia
partial pressure-Thermal shocks)
• Material parameters (Al-Cr-V-Mo are
beneficial and Ni- Si- Mn- are detrimental)

Case studies - Description of damage

Ammonia plant no.1 and 2 which were designed

by M.W.Kellogg were faced with Nitriding attack
in their converters. Ammonia no. 1 was
commissioned on 1969 but after about three years

AMMONIA TECHNICAL MANUAL 184 2010

 major problem occurred in the converter and it
was completely replaced by a new one. Sample A
& B refer to this converter (Fig. 2).

In October 1992 during internal inspection of

converter (Ammonia no. 1) which was opened for
catalyst replacement, we encountered major
Nitridation on thermal barrier bellow 4th bed.

In April 2004 ammonia plant no.2 had a

turnaround for rehabilitation of the converter
basket. Samples C&E refer to this converter (Fig.
2). Formerly flow direction was axial and now is
combination of axial and radial (Ammonia
Casale).

In April 2005 the converter internals of ammonia

plant no. 1 were replaced with the same type of
converter internals as ammonia plant no 2.
Samples D, F, G, H and I refer to this converter
(Fig. 2).

Figure 2- General view of ammonia converter.

Description converter process (MW Kellogg)

The synthesis gas entered through the bottom of

the converter (Fig. 2). Gas direction is upward
between the HP shell and the basket, to the outer
interchanger shell. Then the gas returns downward
in the shell side of the heat interchanger, and it is
preheated against hot converter effluent inside the
interchanger tubes. The flow passes downward
through four catalyst beds in a "catalyst basket."
There is a quench ring in each bed for controlling
the temperature. Then the gas returns upward
through a central pipe and enters the interchanger
(950 °F/510 °C) and leaves the interchanger (550
°F/288° C) from top of the converter.

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 Case study A & B:

As already described, ammonia converter (plant

no. 1) was replaced due to major problems after
three years service. One tube was removed from
interchanger for metallurgical investigation (Fig.
2 and Fig. 5). Two samples were selected from
different heights of the tube. Sample A (Fig.3-left)
was on top of the tube (tubeside outlet) where the
temperature is about 500°F/260°C and sample B
(Fig.3-Middle) was from bottom tube (tubeside
inlet) where the temperature is about 900°F/482°C Figure 5 - Cross section of tube sample B.
as shown in Fig. 2. Tube material was AISI 304 -
1/2" -7M length-BWG 18 (1.25mm). Sample A Case study C&E:
was nonmagnetic but sample B was magnetic as
shown in Fig. 3. Figure 4 shows a cross section of Sample C was removed from the ammonia
tube (Sample A). No sign of Nitriding layer. converter (plant no.2) interchanger (bottom
section) in April 2004 after 21 years as shown in
Fig. 2. Tube material was AISI 316 -1/2 " -7M
length-BWG 18 (1.25mm) based on chemical
analysis. The sample was magnetic as shown in
fig. 3 (Right). A cross section of the tube is
shown in Fig. 6. Nitriding layer is about 0.33mm
thick.

Figure 3-samples of interchanger's tubes

Figure 6- Cross section of tube sample C. Nitriding

layer is visible on inside the tube

This sample is the bottom tubesheet of the

Figure 4- cross section of tube sample A. interchanger on ammonia no. 2 (Fig. 2 & Fig. 7).
Material is AISI 316, 62.5mm thickness.
Figure 5 shows a cross section of tube (Sample
B). Nitriding layer is 0.18 mm.

AMMONIA TECHNICAL MANUAL 186 2010


Figure 7- Bottom tubesheet of interchanger plant no. 2
The tubesheet was magnetic and hardness was
about 500 BHN and it was as brittle as glass (Fig.
8).
Figure 8 - Tubesheet hardness about 500 BHN
Case studies D, F, G, H, I:
In April 2005, all internals of ammonia converter
(plant no.1) and interchanger were removed for
rehabilitation (after 25 years). Samples D, F
through I were selected (Fig. 2).
Sample D was removed from the (bottom section
of tube) as shown in Fig. 2. Tube material was
AISI 316 -1/2 ' -7M length-BWG 18 (1.25mm)
based on chemical analysis. This sample was
magnetic. A cross section of tube is shown in Fig.
9. Nitriding layer is 0.33mm.
2010
Figure 9 - Cross section of tube sample D.
Nitrated layer is shown on tube ID.
Sample F was a distributor which was installed
below the quench ring. Chemical analysis showed
that the material was AISI 310-Thk. 6.00mm and
it didn't absorb the magnet (Fig. 10). Hardness of
this sample was 150 BHN.
Figure 10 - Cross section of sample F.
Distributor ring
Sample G is first bed bottom (Fig.11). Material
was AISI 316, 25mm thickness. Hardness
measurement was done on surfaces and middle
cross section, 220 and 130 BHN respectively. The
sample was magnetic.
Figure 11 - Cross section of sample G, a piece of
1st bed bottom, ammonia plant no. 1
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 Sample H is a thermowell which protect
thermocouple in the ammonia converter. Material
is AISI 321 - 6mm thickness. Outside Diameter
hardness is about 290 BHN and it absorbs magnet
but the hardness of inside diameter is about 140
BHN and nonmagnetic as cast.

Figure 12- Cross section of sample H,

thermowell

Sample I was thermal barrier which was installed

below the 4th bed. (Fig 2). Material was AISI 316
– 1 mm thickness. This sample was as brittle as
glass and numerous cracks are visible in Fig. 13.
It was magnetic and completely nitraded.

Figure 13 - Cross section of sample I,

numerous cracks are visible on surfaces

AMMONIA TECHNICAL MANUAL 188 2010

 Investigations
Table 1 is a summary of all case studies which
were removed from three ammonia converters
(M.W Kellogg) and their interchangers for further
investigations. Sample A was not magnetic and
had no Nitriding layer. The main reason was that
the temperature on this location was low (Tube
side outlet temperature is about 500 F°)
Rate of Nitriding for AISI 304 (Sample B) is 0.06
mm/year. Nitridation rate for AISI 316 (Sample
C) is 0.012 mm/year and the rate for sample D is
0.01mm/year.

Depth of Thickness of
Exposure Hardness Magnetic
Sample Material nitrated layer material
Time (Year) BHN properties
(mm) (mm)
AISI
A. Tube 3 I.M. Nil 1.25 Non magnetic
304
AISI slightly
B. Tube 3 100 0.18 1.25
304 Magnetic
AISI
C. Tube 21 I.M. 0.33 1.25 Magnetic
316
AISI
D. Tube 25 I.M. 0.33 1.25 Magnetic
316
E. AISI
21 500 I.M. 62.5 Magnetic
Tubesheet 316
F. AISI
25 150 Nil 6.00 Non magnetic
Distributor 310
G. AISI Surface:220 Magnetic
25 0.18 25.00
Bottom bed 316 Core:130 Nonmagnetic
H. 290 O.D. Magnetic
AISI 321 25 0.13 8.00
Thermowell I.D. 140 Nonmagnetic
I. Thermal Completely Magnetic
AISI 316 25 1.00 1.00
barrier nitrated 100%

Table 1 - Nitriding attack of various materials in ammonia converters (M.W.Kellogg)

Removing a piece on sample E (tubesheet) was Figure 15 shows microstructure of thermowell

impractical, therefore we couldn't measure the
Nitriding layer but the hardness was about 500
BHN and the surface was as brittle as glass.
The distributor (sample F) didn't absorb the
magnet and the hardness was same as original and
no Nitrated layer was seen on the surface. The
main reason for this phenomenon was material
AISI 310 with higher Ni content.
(sample H). A thin Nitriding layer is visible.
Depth of Nitriding on this material (AISI 321) is
0.13mm.
The last sample (I) was thermal barrier which was
completely Nitrited and it was as brittle as glass
due to low thickness and vulnerable material AISI
316.

Both surfaces on sample G were Nitrited but

inside was as cast. Fig. 14 shows a cross section
and Nitriding layer which are very thin on the
surfaces. Depth of Nitriding is about 0.18mm.

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Figure 14 - Cross section of sample G,
cross section of 1st bed bottom
Figure 15 - Cross section of sample H,
cross section of thermowell
Conclusion
• Investigations on samples A & B which were
selected from top and bottom of one tube
proved that high temperature has a strong
negative effect in the Nitriding of stainless
steels.
• The Nitrited layer is hard and brittle, visible
and mainly consists of Chromium Nitride
which is simply distinguished from base
metals.
• When designing, be careful of low thickness
material, additional corrosion allowance to be
added for Nitridation.
AMMONIA TECHNICAL MANUAL
• Based on the results of this paper, suitable
material for converter are AISI, 310, 321, 316
and 304 by priority.
• Thermal shock: During long periods
influenced the Nitriding rate.
• The Nitriding rate depends on:
1. Ni content - an increase in content in the
alloy, decreases the rate of Nitriding.
2. Temperature - The higher temperature
causes higher Nitriding rate.
3. Pressure - effect of pressure is
unremarkable compare to temperature, but
by increasing ammonia or nitrogen partial
pressure/concentration, Nitriding rate
increased.
Acknowledgment
Thanks and appreciation to my best friend Mr.
Giel Notten- NTT consultancy and my colleagues
in Inspection department of RPC (Mr.
Ebrahimzadeh, and Ms. Ashna) and Mr. Soltani
for co-operations and their advices in preparation
of this paper. Special thanks to RPC’s
management, Mr. Dashti and Mr. Bardideh, for
their advice and support.
References
• Metal Handbook 9TH Vol. 11. Failure analysis
and prevention (ASM)
• High temperature corrosion of engineering alloy
(ASM). By: George Y. Lai
• Behavior of Stainless Steel in hot ammonia
atmosphere – CORROSION NACE (April 1961)
• On the corrosion behavior of Stainless Steel in
ammonia synthesis atmosphere Vol. 20 -1960)
• Investigation of Nitriding mechanism at transition
metal surface: NH3 adsorption and decomposition
on Fe, Ni, Cr. By: Hansong Chang, David B.
Reister - Journal of physic.
• Ammonia, the chemical assignment2.
Environmental and Industrial Chemistry Submitted
by: Jenny Stafford, Angela Stafford, Greta Kyllo-
Mayville State University
• Choose material for H.T. environments By: Peter
Elliot - CEP Feb2001
190 2010
 • Ammonia Casale S.A papers – 1995
• Practical Nitriding and Ferritic Niticaborizing –
ASM 2003
• Lifetime assessment of NH3 plants –paper no. 1C
–AIChE 2001
• www.heattreatmentnews.com
• Ammonia gas Nitriding of Fe-18Cr-8Ni alloy at
lower than 823 K.
• Journal of Material science 25 (1990).
• Corrosion Engineering Guide - KCI Publishing.
Giel Notten-NTT consultancy

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