Anti-Corrosion Methods and Materials: Article Information

Anti-Corrosion Methods and Materials
Failure analysis of catalytic steam reformer tubes

H.M. Tawancy A. Ul-Hamid A.I. Mohammed N.M. Abbas
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To cite this document:
H.M. Tawancy A. Ul-Hamid A.I. Mohammed N.M. Abbas, (2005),"Failure analysis of catalytic steam reformer tubes", Anti-
Corrosion Methods and Materials, Vol. 52 Iss 6 pp. 337 - 344
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Failure analysis of catalytic steam reformer
tubes
H.M. Tawancy, A. Ul-Hamid, A.I. Mohammed and N.M. Abbas
Center for Engineering Research, Research Institute, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
Abstract
Purpose – To determine if the interim use of liquid waste as a fuel in a catalytic steam reformer unit had any deleterious effect on the long-term life of
the reformer tubes.
Design/methodology/approach – Standard metallographic techniques were used to prepare representative samples obtained from various sections
of the reformer tubes for metallurgical evaluation. Microstructural characterization was carried out in a scanning electron microscope equipped with an
energy dispersive X-ray spectrometer. Imaging and elemental analysis was used for the identification of the alloy material, corrosion products and other
microstructural features.
Findings – Hydrogen was produced in a catalytic steam reformer by cracking methane using natural gas as a fuel. Corrosion of reformer tubes occurred
when natural gas fuel was replaced with a liquid waste. Use of liquid fuel waste accelerated the rate of oxidation at the outer tube surface. However,
foreign species from the fuel were not transported into the tube material. The heat-resistant steel casting used for this application was susceptible to
precipitation of Si-stabilized Ni-Nb Laves phase, thus reducing rupture life of the component. Voids at grain boundaries indicative of creep damage were
observed.
Practical implications – Although, the interim use of liquid waste fuel appeared not to have damaged the tubes, it was concluded that the expected
service life of the tubes may not be realized because of the susceptibility of the material to precipitation of Laves phase. An Fe-base superalloy UNS
N08810 or UNS N08811 was recommended as a replacement material for this application.
Originality/value – This paper provides an account of a failure analysis study. It identifies incorrect materials selection for a particular application and
suggests better alternative along with its justification. The information is deemed useful for plant designers and engineers working in the related
industry.
Keywords Corrosion, Wastes, Fuels, Boiler tubes
Paper type Research paper
Introduction temperature of the tubes was 9508C. There was a variation in

temperature from the top to bottom end of the tube, with the
Catalytic steam reformer units are used in the petrochemical top section being hotter.
industry to produce hydrogen. This is accomplished by the Typically, the tubes are designed to last 100,000 h (11.4
cracking of methane in catalysis tubes that are maintained in a years) for this kind of application. The objective of this
vertical position and externally heated by burners. In the case investigation was to determine if the long term service life of
considered here, natural gas was used as a fuel to provide the the reformer tubes could have been affected by using the
thermal energy required for the process, following the liquid fuel. Six samples obtained from different regions of the
manufacturer’s recommendation. However, the plant started tubes were evaluated for this purpose.
using waste liquid (a by product of the cracking process) as a
fuel instead of natural gas. After two weeks of operation
following the switchover, a corrosion product developed at the Methodology
external tube surface. The corrosion product was not Metallographic specimens were prepared from the various
adherent and most of it could be washed away. sections of the tube using standard techniques.
Catalysis tubes were 102 mm in internal diameter and Microstructural characterization was carried out in a
9-10 mm in wall thickness. The tubes were made of a French scanning electron microscope equipped with an energy
grade of heat-resistant steel casting with a chemical dispersive X-ray spectrometer (atmospheric thin window)
composition shown in Table I. Internal gas pressure of the capable of detecting light elements down to carbon with a
cracking process was about 30 atm, and the flame temperature detection limit of 0.2 weight percent. Imaging was performed
of the burner was approximately 1,1008C. Average external using both secondary and backscattered electrons at an
accelerating voltage of 20 keV.
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Results
The current issue and full text archive of this journal is available at
www.emeraldinsight.com/0003-5599.htm Visual inspection
Visual inspection of the tube did not reveal wall thinning
while the scale developed at the outer and inner surfaces of
Anti-Corrosion Methods and Materials
52/6 (2005) 337– 344
q Emerald Group Publishing Limited [ISSN 0003-5599] The authors wish to acknowledge the support of the Research Institute of
[DOI 10.1108/00035590510624677] King Fahd University of Petroleum and Minerals.
337
Failure analysis of catalytic steam reformer tubes Anti-Corrosion Methods and Materials
H.M.Tawancy, A. Ul-Hamid, A.I. Mohammed and N.M. Abbas Volume 52 · Number 6 · 2005 · 337 –344
Table I Nominal and measured chemical composition (wt percent) of quantifying the spectral data and the nominal composition of
the reformer tube material the tube material which was a French grade of heat-resistant
steel casting. Within the relative accuracy of the analysis, it
Chemical composition (wt percent) was observed that the measured composition is in agreement
Element Nominal Measured with the nominal composition. Elements not detected,
Fe Bal. 46.72 particularly C and Mn, were mostly present in the form of
Ni 23-25 25.01 secondary phases (carbides and sulfides, respectively).
Cr 24-26 24.59
Nb 1.4-1.8 2.11 Metallurgical evaluation of the tube material
Si 0.5-1.5 1.57 Gross microstructural features along a cross-section of the
Mn 1a ND tube are summarized in the light optical micrographs of
C 0.25-0.35 ND Figure 3. Consistent with the visual inspection, the depth of
S 0.03a ND corrosion attack below the outer surface (Figure 3(a)) was
P 0.03a ND greater in comparison with the inner surface (Figure 3(c)).
Pb 0.01 ND Internal attack occurred primarily at grain boundaries as
Sn 0.01 ND shown in Figure 3(a). Voids were observed along the cross-
section particularly at grain boundaries suggesting creep
Notes: aMaximum; ND: not detected damage, which could be related to precipitation of Laves
phase, as shown later.
A typical morphology of the scale formed at the outer tube
the tube was well adherent. However, the outer tube surface surface is shown in the secondary electron images of Figure 4.
appeared more blackish and rough compared to the inner Ridges within the scale as indicated by the arrows in
surface suggesting greater metal wastage resulting in a Figure 4(a) were indicative of a non-protective scale.
corrosion product.
General structure of the tube is illustrated in the light
optical macrographs shown in Figure 1. Extent of corrosion at ‘. . .the use of liquid waste in place of natural gas
the outer surface was greater than that at the inner surface as
had resulted in the acceleration of corrosion
demonstrated by both the appearance of the outer tube
surface and corresponding depth of attack. Figure 1 also attack at the outer tube surface. . .’
shows the large elongated grains typical of an as-cast
structure. It could be suggested from above observations
that the use of liquid waste in place of natural gas had resulted Figure 5 is an example showing the results of analyzing the
in the acceleration of corrosion attack at the outer tube composition of the surface scale and subscale developed by
surface. the outer tube surface. A typical microstructure of the scale is
shown in the backscattered electron images of Figure 5(a). It
Material verification can be seen that the surface scale was about 40 mm in
An energy dispersive X-ray spectrum illustrating typical thickness and it consisted of three oxides: an outermost layer
elemental composition of the tube material is shown in of a spinel-type oxide likely to be (Fe,Ni)Cr2O4 (Figure 5(b))
Figure 2. Table I shows a comparison between the results of containing particles of a Nb-rich oxide (Figure 5(c)), and an
Figure 1 Light optical macrographs illustrating typical overall structure of the reformer tube cross-section
338
Figure 2 Representative EDS spectrum illustrating the chemical composition of the tube material
Figure 3 Light optical micrographs illustrating gross microstructural Figure 4 Secondary electron images illustrating typical morphology of
features along the tube cross-section; (a) structure near the outer the scale formed at the outer tube surface; (a) ridges are indicated by
surface; (b) structure of the middle section and (c) structure near the arrows; and (b) same region at a higher magnification
inner surface
understood in terms of its less protective nature in comparison

with Cr2O3. Also, oxides enriched in refractory elements are
known to be non-protective and could lead to decohesion of the
inner layer of a Cr-rich oxide (Figure 5(d)) expected to be scale (Smialek and Meier, 1987). Voids were observed at the
Cr2O3. scale-metal interface as well as at grain boundaries as shown by
As can be seen from Figure 5(a), the spinel-type oxide the arrows in Figure 5(a). However, at other locations these
appeared to be detached and losing adherence, which could be voids contained a Cr-rich oxide expected to be Cr2O3.
339
Generally, the maximum depth of attack was in the order of material contained any impurities, which could have
50 mm. Niobium-rich precipitate particles were observed near transported from the liquid waste fuel.
the surface as shown in the spectrum of Figure 5(e). As can be A backscattered electron image and corresponding X-ray
seen, the main elemental constituents of the precipitate particles mapping images illustrating the distribution of various
were Fe, Cr, and Nb with a smaller concentration of Ni elements across the surface scale and into the metal are
suggesting that they could be of a sigma-type phase. A spectrum shown in Figure 6. Consistent with the results of Figure 5, the
representative of the tube material is shown in Figure 5(f). In surface scale consisted of an inner layer of a Cr-rich oxide and
general, there was no evidence that either the scale or the tube an outer layer of a spinel-type oxide. Some of the grain
Figure 5 (a) Backscattered electron image and (b, c, d, e, f) corresponding EDS spectra illustrating the microstructure and elemental composition of the
outer surface and cross-section of the tube; voids at the oxide-metal interface and at grain boundaries are indicated by arrows in (a)
340
Figure 6 (a) Backscattered electron image and corresponding X-ray Figure 7 Backscattered electron image and corresponding X-ray
mapping images illustrating the distribution of various elements mapping images of various elements illustrating the presence of
across the scale formed at the outer surface and into the tube Cr-rich oxide and Nb-rich phase at grain boundaries near the outer
material tube surface
boundary voids, however, were found to contain Nb-rich outer scale had resulted in the formation of a soluble
precipitates. corrosion product. As expected of a high Ni steel containing
Another example is given in Figure 7 showing the presence Nb and relatively high Si concentration, the tube material was
of Nb-rich precipitates and Cr-rich oxide at grain boundaries susceptible to precipitation of a Laves phase of the type
near the outer surface. Nb2Ni3Si as shown in Figure 10.
Figure 8 shows the results of analyzing the subscale at
another location where the grain boundaries of the metal
‘. . .it was evident that internal oxidation had
contained a Cr-rich oxide. A typical morphology of the
subscale is shown in the secondary electron image of taken place indicating that the surface scale
Figure 8(a), and a corresponding backscattered image is became non-protective. In contrast, the scale
shown in Figure 8(b). An energy dispersive X-ray spectrum developed by the inner surface was more dense
representative of the internal oxide at grain boundaries and compact. . .’
(region 1 in Figure 8(b)) is shown in Figure 8(c). It is evident
from the results of quantifying the spectral data (Table II) that It is observed from the secondary electron image of
the oxide was of the type (Cr,Fe)2O3. Figure 10(a) that the Laves phase assumed a lamellar
It could be concluded from the above observations that the morphology, which is known to be detrimental to creep-
tube material was able to develop a surface layer of Cr2O3 as rupture strength (Wallwork and Croll, 1976). An energy
expected. However, this scale was outgrown by a less dispersive X-ray spectrum representative of the Laves phase
protective layer of a spinel-type oxide. Also, it was evident and the results of quantifying the spectral data are shown in
that internal oxidation had taken place indicating that the Figure 10(b).
surface scale became non-protective. In contrast, the scale Within the relative accuracy of the analysis, the composition
developed by the inner surface was more dense and compact of the precipitate can be seen to approach that of
as shown in Figure 9 reflecting a higher protective nature in Nb2(Ni,Fe,Cr)3Si. Occasionally, particles of manganese
comparison with the scale developed by the outer surface. sulfide were also observed (Figure 10(c)). It is well known
In summary, the above results suggest that the use of liquid that an important function of Mn is to combine with S
waste as a fuel had accelerated oxidation rate at the outer tube forming manganese sulfide. If present as iron sulfide, S causes
surface resulting in a non-protective scale. It would appear hot-shortness (cracking during hot-working). In contrast,
that the reaction between the products of combustion and the manganese sulfide does not have this deleterious effect.
341
Figure 8 (a) Secondary electron image of the tube cross-section; (b) corresponding backscattered electron image; and (c) EDS spectrum obtained from
the internal oxide
Evidently, the grain boundary voids observed in Figure 3 moderately carburizing but coke is not formed
could have resulted from creep damage accelerated by (Blackburn, 1981). In the present case, a well adherent
precipitation of the Laves phase. scale was observed at the outer and inner surfaces of the
catalytic steam reformer tube that also showed no evidence of
wall thinning. However, a rough texture, formation of a
Discussion blackish corrosion product and a greater depth of corrosion
It is well known that the environment resulting from burning attack pointed towards excessive metal wastage at the outer
natural gas is rather simple where oxidation is the only mode tube surface compared to the inner surface. The outer surface
of corrosion attack (Tawancy, 1993). Also, the environment developed a protective surface layer of Cr2O3. However, this
within catalytic steam reformer tubes is known to be scale was outgrown by a less protective layer of a spinel-type
(Fe,Ni)Cr2O4 oxide. Observations of ridges within the scale
and of internal oxidation within the alloy also indicated that
the surface scale was non-protective. Lack of scale adherence
Table II Chemical composition (atomic percent) of the oxide had resulted in its detachment from the alloy surface while
voids were observed at the scale-metal interface as well as at
Element Chemical composition (atomic percent)
grain boundaries.
Cr 24.55 These findings suggested that the use of liquid waste in place
Fe 8.50 of natural gas had, in fact, resulted in a relatively high rate of
Ni 5.76 corrosion attack at the outer tube surface resulting in a non-
O 61.19 protective scale. On the other hand, the dense and compact
scale developed by the inner surface retained its highly
342
Figure 9 (a) Secondary electron image and (b) corresponding EDS spectrum illustrating the morphology and elemental composition of the scale formed
at the inner tube surface
protective nature. However, formation of a non-protective limited to a maximum of 1.8 percent (Blackburn, 1981). In
oxide at the outer surface due to the interim use of liquid waste the present case, a proper material was selected for the
fuel is not likely to affect the long-term service performance of application on the basis of the 100,000 h creep-rupture
the reformer tube. The service life of this component is more strength. However, relatively high Si content (approaching the
likely to be affected by the presence of high Si content present in upper limit of specification) in Ni þ Nb containing alloy was
the alloy material, as shown below. found to stabilize Laves phase of the type Nb2(Ni,Fe,Cr)3Si.
Typically, materials for catalytic steam reformer The composition and lamellar morphology of the precipitated
applications are selected on the basis of 100,000 h creep- Laves phase is typically detrimental to creep-rupture strength
rupture strength, limiting the choice to a small group of high (Wallwork and Croll, 1976). Although a binary Ni-Nb Laves
Ni steels strengthened by Cr-rich carbides. Because of the phase is not thermodynamically stable, it is known to be
associated limited ductility, these steels can only be processed stabilized by Si. Precipitation of the Laves phase accelerates
by casting. Further strengthening can be provided by addition creep damage as indicated by the formation of grain boundary
of refractory elements such as Nb and W. Also, such steels voids. Typically, precipitation of lamellar Laves at grain
may contain a high Si concentration (1.8-2 weight percent) to boundaries proceeds very rapidly at elevated temperatures by
improve the carburization resistance. a discontinuous mechanism involving grain boundary
However, it is important to note that Si can stabilize migration. This occurs when precipitation within the grains
topologically close-packed (TCP) Laves phases of the type is rather slow, and therefore the free energy difference
Nb 2Ni 3Si and W 2 Ni3 Si degrading weldability, room between the grain boundary and grain interior can increase to
temperature ductility as well as creep-rupture strength. In an extent that causes the grain boundary to migrate.
the case of steels strengthened by W, the amount of Si is Furthermore, coarsening of the initially precipitated phase
343
Figure 10 (a) Secondary electron image of lamellar precipitates at can occur more rapidly than nucleation of additional phase
grain boundaries (marked 1) and discrete particles in the matrix and at causing depletion of Nb on both sides of the grain boundaries.
the grain boundaries (marked 2); (b) EDS spectrum derived from Some intragranular precipitation of Laves phase can occur
lamellar precipitates along with elemental composition shown in the leaving behind a precipitate free zone associated with localized
inset and (c) EDS spectrum obtained from discrete particles Nb depletion. Creep rate could be accelerated in those
relatively weaker zones contributing to grain boundary
embrittlement.
Therefore, in summary, it is suggested that the
susceptibility of the tube material to precipitation of lamellar
Laves phase at grain boundaries could shorten the creep-
rupture life to 50,000 h or even less.
Conclusions
It could be concluded from the results of this investigation
that the use of liquid waste fuel could accelerate the
oxidation rate of the tube material. Provided that the use of
this fuel had been temporary, no long-term detrimental
effect would be expected. However, use of a Nb
strengthened high Ni steel that contains a relatively high Si
concentration could possibly substantially reduce the creep-
rupture life of the component. Since the Si levels required to
stabilize Laves phase in various alloys are not known, it is
not possible to envisage a Si level at which precipitation of

Laves phase is suppressed to the extent of maintaining
rupture ductility.
However, a moderately carburizing environment, such as
that encountered in the present case, does not warrant the use
of steel with a high Si content. Based on previous experience,
the use of one of the Fe-base superalloys such as INCOLOYw
alloy 800H (UNS N08810) or 800HT (UNS N08811) for
this application can realize most of the expected service life
(i.e. 100,000 h).
References
B1ackburn, J. (1981), Carburization in High Temperature
Process Plant Materials Colloquium Proceedings,
Coordinator: Norton, J., (Commission of the
European Communities, Report No. EUR 7773,
Luxembourg), p. 7.
Smialek, J.L. and Meier, G.H. (1987) in Sims, C.T., Stoloff,
N.S. and Hagel, W.C. (Eds), Superalloys IT, Wiley
Interscience, New York, NY, p. 312.
Tawancy, H.M. (1993), Structure and Properties of High
Temperature Alloys: Applications of Analytical Electron
Microscopy, KFUPM Press, Dhahran, p. 251.
Wallwork, G. and Croll, J. (1976) in Newkirk, J. (Ed.),
Reviews of High Temperature Materials, III, Freund
Publishing House, London, p. 108.
344
This article has been cited by:
1. Jaganathan Swaminathan, Prabha Prasad, Manoj Kumar Gunjan, Krishna Gugloth, Prabir Kumar Roy, Raghubir Singh,
Rabindranath Ghosh. 2008. Mechanical strength and microstructural observations for remaining life assessment of service
exposed 24Ni–24Cr–1.5Nb cast austenitic steel reformer tubes. Engineering Failure Analysis 15:6, 723-735. [CrossRef]

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Anti-Corrosion Methods and Materials

Failure analysis of catalytic steam reformer tubes

*Related content and download information correct at time of download.

Keywords Corrosion, Wastes, Fuels, Boiler tubes

Paper type Research paper

Introduction temperature of the tubes was 9508C. There was a variation in

understood in terms of its less protective nature in comparison

not possible to envisage a Si level at which precipitation of

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