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On The Degradation Modes of Various Steel Grades Used in Heat Recovery Systems: An Application From The Petrochemical Industry
On The Degradation Modes of Various Steel Grades Used in Heat Recovery Systems: An Application From The Petrochemical Industry
(2017) 6:36–43
DOI 10.1007/s13632-016-0329-2
TECHNICAL ARTICLE
Received: 11 November 2016 / Revised: 14 December 2016 / Accepted: 15 December 2016 / Published online: 29 December 2016
Springer Science+Business Media New York and ASM International 2016
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Metallogr. Microstruct. Anal. (2017) 6:36–43 37
Experimental Procedure
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38 Metallogr. Microstruct. Anal. (2017) 6:36–43
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Metallogr. Microstruct. Anal. (2017) 6:36–43 39
adhering to the internal surface where C is seen to be the the as-received condition as demonstrated in the example of
major elemental constituent consistent with a layer of coke. Fig. 6. A bright-field STEM image of the ash is shown in
Figure 4 summarizes the results of analyzing the smaller Fig. 6a. Corresponding microdiffraction patterns consistent
pits observed at the internal surface of the pipe in the as- with the hexagonal structure of graphite in [001] and [1-26]
received condition. Pits about 5 lm in diameter can be orientations are shown in Fig. 6b and c, respectively. As shown
observed in the backscattered SEM image shown in in the EDS spectrum of Fig. 6d, C is the essential elemental
Fig. 4a. A corresponding EDS spectrum of the area in constituent of the ash, as expected.
Fig. 4a is shown in Fig. 4b where the major elemental Metal dusting is known to result from an aggressive
constituents are observed to be Fe and C with smaller carburizing environment, which enhances the formation of
concentration of O. The corresponding x-ray mapping graphite and powders of metal carbides [5, 6]. Apparently,
images of Fe, O and C are shown in Fig. 4c, d, and e, there has been some leakage of the reformed carbonaceous
respectively. gas into the connecting pipe. On the other hand, metal
The above observations indicate that the inner surface of the dusting is known to occur at temperatures in the range of
pipe has been degraded by metal dusting. This is further con- 350–900 C. Therefore, it appears that the temperature at
firmed by the results of x-ray diffraction analysis. Figure 5 location 1 in Fig. 1 has been higher than the normal tem-
shows an x-ray diffraction pattern obtained from the blackish perature, which is said to be about 200 C. Although the
powdery deposit observed at the internal pipe surface as well as exact mechanism of the metal dusting of carbon and low-
standard diffraction patterns of cementite (Fe3C; orthorhom- alloy steels is still subject to debate [6–10], it is believed
bic: a = 0.452 nm, b = 0.507 nm, c = 0.674 nm), graphite that the decomposition of cementite (Fe3C) into iron and
(hexagonal: a = b = 0.247 nm, c = 0.680 nm), ferrite carbon may play a key role [7, 8].
(body-centered cubic: a = 0.287 nm) and magnetite (Fe3O4; In contrast with the damage sustained by the low-alloy
cubic: a = 8.39 nm). It is observed that most of the diffraction steel pipe at location 1 in Fig. 1, and described above, the
maxima can be interpreted in terms of the structures of graphite bypass low-alloy steel pipe near the stainless steel pipe
and cementite. Some ashes removed from the internal surface (location 2 in Figs. 1 and 2b) is found to be degraded by
of the pipe were found to be transparent to electrons at 200 keV oxidation, as summarized in Figs. 7 and 8. The morphol-
and therefore have been suitable for TEM/STEM analysis in ogy of the oxide observed at the internal surface is
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40 Metallogr. Microstruct. Anal. (2017) 6:36–43
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Metallogr. Microstruct. Anal. (2017) 6:36–43 41
the weld seam in the section of elbow received for analysis. martensitic structure [13]. However, a proper post-welding
A possible solution for the above problem is to use steel heat treatment of 304 stainless steel may also be considered
more resistant to fatigue such as that with a tempered as an alternative solution.
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42 Metallogr. Microstruct. Anal. (2017) 6:36–43
Conclusions
The present study has shown that the low-alloy steel pipe
near the reboiler has been degraded by metal dusting
while the low-alloy steel pipe fitted in the stainless steel
pipe has been degraded by oxidation. Although leakage of
the carbonaceous reformed gas may have promoted metal
dusting, a replacement steel grade more resistant to oxi-
dation and metal dusting may be considered for the
application, such as that characterized by the composition
%Cr ? 2%Si [ 24 wt%. Cracking at the weld seam of the
elbow made of 304 stainless steel is found to occur by a
fatigue mechanism and, therefore, a tempered martensitic
steel may be more suitable for the application. On the
other hand, it is possible that a proper post-welding heat
treatment of 304 stainless steel could provide a solution to
Fig. 9 Secondary electron SEM image showing the major crack in the problem.
the weld seam of the sample shown in Fig. 2c (welded elbow of 304
stainless steel)
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Metallogr. Microstruct. Anal. (2017) 6:36–43 43
Acknowledgment It is pleasure to acknowledge the continued sup- 7. M. Szkodo, G. Gajowiec, Studies of the mechanism of metal
port provided by King Fahd University of Petroleum and Minerals. dusting of 10CrMo9-10 steel after 10 years of operation in the
semi-regenerative catalytic reformer. Corros. Sci. 102, 279–290
(2016)
8. H.M. Tawancy, Degradation of C-1/2Mo steel pipe by metal
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