JFAPBC (2005) 4:54-61 © ASM International

DOI: 10.1361/154770205X55063 1547-7029 / $19.00

Failure of Ethylene Furnace Outlet Transfer Line Due to Overheating (continued)

Failure of Ethylene Furnace Outlet Transfer Line

Due to Overheating
A. Ul-Hamid, H.M. Tawancy, A.I. Mohammed, S.S. Al-Jaroudi, and N.M. Abbas
(Submitted April 23, 2005; in revised form June 29, 2005)
An outlet transfer line tube of an ethylene-cracking furnace failed after five years of service. The tube, made
from Incoloy alloy 800H, developed cracks that penetrated the entire thickness. Optical and scanning electron
microscopy, X-ray diffraction, and microhardness tests were used to evaluate the failed tube. It was found
that the tube was considerably embrittled by high-temperature carburization, leading to intergranular fracture
at the inner surface. Carburization appeared to have been caused by high-temperature exposure to the carbon-
rich atmosphere associated with the coke adhered to the inner surface. Additionally, the decrease in heat
transfer due to the coke deposits caused the wall temperature to increase during service. However, at the
outer surface, the tube fractured by a fatigue process that could result from the use of a counterweight to
prevent sagging of the tube as a result of the coke deposition. Based on the results obtained, a short-term
solution was to modify various process parameters to reduce the extent of coke deposition and/or increase the
frequency of decoking and to discontinue the use of a counterweight. However, the long-term solution is to
replace alloy 800H.

Keywords: carburization, fatigue, SEM, transfer line

Introduction cause carburization. Adherent coke is removed at

Ethylene (C2H4) was produced in an industrial intervals by a decoking process, where the
petrochemical plant by cracking ethane (C2H6) in a hydrocarbon feed is shut off and a mixture of air
pyrolysis furnace externally heated to 1050 to 1100 and steam at approximately 300 °C is passed through
°C. Products of the cracking reaction, including the furnace. As a result, some of the coke is burned
uncracked ethane, were carried into an outlet transfer away, and some is cracked off and blown away.
line located between the furnace outlet and the During decoking, however, the system can be subject
primary transfer line exchanger (PTLE), as to thermal shock and creep damage.
schematically illustrated in Fig. 1. According to
design specifications, the outlet transfer line was
made of Incoloy alloy 800H (UNS N08810) having
a tube wall thickness of 12.7 mm (½ in.).
It is well known that the process of producing
ethylene generates free carbon according to the
reaction:[1]
C2H4 ↔ CH4 + C
Carbon generated by this reaction is deposited as
adherent coke at the inner surface of furnace
components. Deposition of coke can have two detri-
mental effects. First, it acts to retard heat transfer,
thus requiring a higher furnace wall temperature to
maintain the same gas temperature. Secondly, it Fig. 1 Schematic illustration of the outlet transfer line showing
provides the carbon-rich environment necessary to the location of the failure

A. Ul-Hamid, H.M. Tawancy, A.I. Mohammed, and N.M. Abbas, Center for Engineering Research, Research Institute, King Fahd
University of Petroleum & Minerals, P.O. Box 1073, Dhahran 31261, Saudi Arabia. S.S. Al-Jaroudi, Saudi Aramco, P.O. Box 65,
Tanajib, Saudi Arabia. Contact e-mail: anwar@kfupm.edu.sa.

54 Volume 5(4) August 2005 Journal of Failure Analysis and Prevention

 Massive deposition of coke increases the weight lurgical evaluation. Microchemical analysis by
of the tube. To prevent tube sagging of the outlet energy-dispersive X-ray spectroscopy (EDS) in a
transfer line during coke deposition, a spring-type scanning electron microscope (SEM) was used to
weight support was used, as shown in Fig. 1. verify the tube material. Structural analysis of the
However, later on, the spring design of the support surface scale as well as the tube material was con-
was modified into a counterweight around the tube ducted using X-ray diffraction (Cu-Kα radiation).
(Fig. 1). This modification was designed to reduce Both optical metallography and SEM were used in
stresses at the PTLE inlet cone to the elbow weld, microstructural characterization. Fractography was
which had a history of cracking. This was followed conducted in an SEM, and Vickers microhardness
by installation of a new tube that remained in service tests were used to evaluate the mechanical strength.
for 5 years, after which the furnace was shut down
for repair. During the 5 years of service, the furnace Results and Discussion
was subject to 18 decoking processes. After the repair, Visual Inspection
the transfer line was inspected using external dye Visual inspection of the as-received section of the
penetrant techniques, and no cracks were detected. transfer line tube revealed the absence of wall
However, within 1 h after starting operation, a leak thinning and confirmed that little or no corrosion
and fire were observed near the transfer line tube took place during service. As illustrated in the
and into the flange weld. Cracking of the tube was photograph in Fig. 2(a), the tube thickness
detected in the region of the counterweight at approached 12.7 mm (½ in.), as per design speci-
approximately 12.7 cm (5 in.) from the weld, as fications. A major transverse crack that had pene-
shown in Fig. 1. trated the entire tube thickness was observed, as
shown in Fig. 2(b) and (c). There was no evidence
Experimental Procedure that the fracture was preceded by macroscopic plastic
Selected specimens were prepared from as-received deformation, and the crack followed a zigzag path
sections of the failed pipe and were used for metal- that branched at various locations, such as “A” in Fig.
2(d). These obser-
vations are consistent
with macroscopically
brittle intergranular
fracture. In addition to
the major crack, other
minor cracks were
observed, for example,
at “B” in Fig. 2(d).
(a) (b) Although the stresses
resulting from gas
pressure in the ethylene-
cracking process are
relatively low, previous
experience shows that
the most common
failure modes of furnace
components are
longitudinal creep
rupture and carburi-
(c) (d) zation. [1] Transverse
cracking, however, as
Fig. 2 Photographs of (a) cross section indicating the absence of wall thinning, (b) inner surface
illustrating a major crack that had penetrated the entire thickness, (c) outer surface illustrating the
shown in Fig. 2, would
major crack, and (d) inner surface showing branching of crack at “A” and the presence of secondary not be anticipated if
cracks at “B” the failure was by creep

Journal of Failure Analysis and Preven- Volume 5(4) August 2005 55

tion
 Failure of Ethylene Furnace Outlet Transfer Line Due to Overheating (continued)

rupture. Creep damage is usually associated with of carburization is considerably accelerated at

frequent decoking, while carburization is associated
with infrequent decoking. In the present case, the
furnace was subject to an average of one decoking
operation every 14 weeks. This relatively low decok-
ing frequency could promote the carburization.[1]
temperatures above approximately 925 °C.[2,3]
Characterization of Surface Scale
An example of the analysis of the scale formed at
the inner surface of the tube is given in Fig. 4. Two

Materials Verification
The SEM/EDS analysis provided data that were
consistent with the tube material being alloy 800H.
A representative energy-dispersive X-ray spectrum
derived from the tube material is illustrated in Fig.
3. As can be seen, the main elemental constituents
are iron, chromium, and nickel. Table 1 summarizes
quantitative spectral analysis for comparison with the
nominal chemical composition of alloy 800H. The
measured composition is seen to be in agreement
with the nominal composition of the alloy.
Generally, alloy 800H is one of the alloys recom-
mended for high-temperature applications involving
carburizing environments. In comparison with other (a)

alloys, it has above-average resistance to carburiza-

tion;[2] however, available data shows that the rate

(b)

Fig. 3 EDS spectrum representative of the tube material

Table 1 Nominal and Measured Chemical

Composition of Incoloy Alloy 800H

Chemical Composition, wt.%

Element Nominal Measured(a)
Fe bal 46.66
Ni 33 32.42
Cr 21 20.92
Ti 0.4 ND
Al 0.4 ND (c)
Mn 0.8 ND
Si 0.5 ND Fig. 4 (a) SEM image of the scale morphology. (b) EDS
C 0.08 ND spectrum representative of the regions marked “x” in (a).
(c) X-ray diffraction pattern derived from the surface
(a) ND, not detected
scale compared with standard patterns of Cr2 O 3 and
Fe3 O 4

56 Volume 5(4) August 2005 Journal of Failure Analysis and Prevention

layers of surface scale could be distinguished, as
shown in the secondary electron SEM image of Fig.
4(a). Energy-dispersive X-ray spectra derived from
the outer scale layer did not show any evidence of
high Z elements and are consistent with the layer
being carbon. Figure 4(b) is a spectrum representative
of the inner scale layer marked “x” in Fig. 4(a). As
can be seen, the scale was enriched in chromium and
contained smaller concentrations of iron and nickel.
A corresponding X-ray diffraction pattern is shown
in Fig. 4(c). Many of the observed reflections could
be indexed in terms of the structures of Cr2O 3
(hexagonal: a = 0.496 nm; c = 1.360 nm) and Fe 3O4
(cubic: a = 0.8394 nm). However, the combination
of spectral and X-ray diffraction data suggests that
the scale is a mixture of Cr2O3 and a spinel of the
type Ni(Fe,Cr2)O 4. Structurally, spinels such as
FeCr2O4 (cubic: a = 0.8364 nm) and NiFe 2O4 (cubic:
a = 0.8339 nm) are isomorphous with Fe 3O4; that
(a)
(b)
Fig. 5 (a) Light optical macrograph of the fracture surface
showing regions A and B. (b) SEM image illustrating the
overall morphology of regions A and B in (a)
Journal of Failure Analysis and Preven-
tion
is, they all produce similar diffraction patterns. Solid
solution could produce a spinel of the type
Ni(Fe,Cr)2O4.
Earlier studies of carburization showed that in
severely carburizing environments where the carbon
activity reaches 1, Cr2O3-forming alloys such as alloy
800H develop surface carbide scales rather than oxide
scales. [2] The lack of carbides in the scale suggests
that the oxygen potential of the environment was
high enough to promote the formation of an oxide
scale. However, the scale was not highly protective,
as indicated by the presence of voids in Fig. 4(a) that
permitted penetration of carbon into the alloy
substrate, as demonstrated later.
Fracture Mode
Examination of the macroscopic features of the
entire fracture surface area corresponding to the
major crack of Fig. 2 revealed two distinct fracture
mechanisms, as illustrated in the macrographs of Fig.
(a)
(b)
Fig. 6 SEM images showing (a) region A and (b) region B in
Fig. 5(a)
Volume 5(4) August 2005 57
 Failure of Ethylene Furnace Outlet Transfer Line Due to Overheating
5(a) and (b). Approximately two-thirds of the frac-
ture surface extending from the inner tube surface
was granular (region A in Fig. 5a and b). In contrast,
the remaining one-third extending from the outer
surface contained striations separated by relatively
flat regions (region B in Fig. 5a and b).
Corresponding to region A of Fig. 5(a) and (b),
the fracture mode was found to be intergranular, as
illustrated in the secondary electron SEM image of
Fig. 6(a). However, in region B, the striations
suggested fracture by a fatigue mechanism, as shown
in Fig. 6(b) and further illustrated in Fig. 7(a).
Evidence for localized plastic deformation during
the fatigue process was seen at high magnification
(Fig. 7b). Minor cracks at the inner surface of the
tube (Fig. 2d) were found to be of the intergranular
type, as illustrated in Fig. 8.
It is evident from the previous results that the
transfer line tube was subject to two different pro-
cesses leading to fracture. Carburization resulting in
(a)
(b)
Fig. 7 (a, b) SEM images of fatigue fracture near the outer
surface of the transfer line
58 Volume 5(4) August 2005
(continued)
massive precipitation of carbide phases is known to
cause severe embrittlement, leading to intergranular
cracking.[4,5] This could explain the occurrence of
intergranular fracture at the inner surface of the tube,
as further demonstrated by the results of
microhardness measurements as well as microstruc-
tural characterization presented later. In contrast,
fatigue fracture results from cyclic stresses that are
not normally encountered during the operation of
pyrolysis furnaces. Previous experience shows that
cracking of pyrolysis furnace tubes results from either
embrittlement associated with high-temperature
carburization and/or creep damage. Accordingly, the
most important materials requirements for such
applications are resistance to carburization and long-
term rupture strength.[1] It is possible, however, that
the use of a counterweight, apparently intended to
reduce creep damage, led to the development of
alternating internal stresses at the outer surface of
the tube. Alternating stress conditions leading to
fatigue can be created by the deposition of coke at
the inner surface and by the presence of a counter-
(a)
(b)
Fig. 8 (a, b) SEM images illustrating secondary intergranular
cracks at the inner surface of the transfer line
Journal of Failure Analysis and Prevention
weight at the outer surface. Eventually, the tube was
cracked at the outer surface by a fatigue mechanism.
Reference to the design and operation of ethylene-
cracking furnaces suggests that the use of a counter-
weight is not a recognized practice. [1]
Evaluation of Mechanical Strength
At the inner surface of the tube where the carburi-
zation was most severe, the average hardness was
found to be 287 HV, corresponding to 27 HRC.
However, at the middle section, the average hardness
was reduced to 182 HV (85 HRB). Also, the hard-
ness at the outer surface was 185 HV (87 HRB).
Typically, in the annealed condition, the hardness of
alloy 800H is approximately 72 HRB. Two factors
could contribute to the observed hardening, namely
carburization and thermal aging. Hardening due to
carburization would be expected to be a maximum
near the inner surface where the carbon content
would be the highest, while thermal aging would be
expected to produce the highest hardness near the
outer surface where the temperature was the highest.
Because the maximum hardness was near the inner
surface, the hardening effects were attributed to
carburization.
Earlier studies of the carburization behavior of this
alloy suggested that severe carburization resulting
in considerable loss of ductility occurs at
temperatures above approximately 925 °C.[6] For
example, after 24 h of exposure at 980 °C in a
reducing carburizing environment similar to that
encountered in ethylene cracking, the room-
temperature tensile ductility was reduced from 46
to 5%. However, after the same exposure period in
(a) (b)
Fig. 9 (a to c) SEM images illustrating massive intergranular and intragranular carbide precipitates parallel to the inner surface of the
transfer line (same area observed at different magnifications)
Journal of Failure Analysis and Preven-
tion
air, the tensile ductility was reduced from 46 to 43%.
In contrast, after 24 h of exposure at 925 °C in the
same carburizing environment, the alloy maintained
36% tensile ductility.
Based on the results of hardness measurements and
the known effect of exposure temperature on the
ductility of alloy 800H in carburizing environments,
it appeared that the tube was exposed to a
temperature above approximately 925 °C during
operation. Although the normal operating temper-
ature is 840 to 860 °C, overheating could occur
during the decoking process. [1]
Microstructural Characterization
Representative microstructural features at the inner
surface of the tube are illustrated in the secondary
electron SEM images of Fig. 9(a) to (c). Massive
precipitates can be seen both in the matrix and at
grain boundaries. Voids and cracks were observed
near grain boundaries, as indicated by the arrows.
However, there was no evidence for excessive grain
growth, as indicated by comparison with typical grain
sizes of alloy 800H in the annealed condition.[7] It
is to be noted that the alloy can undergo an
appreciable grain growth above approximately 980
°C.[7] Although the tube appeared to have been
heated above the normal operating temperature, as
pointed out earlier, the microstructures of Fig. 9
suggest that the maximum temperature reached was
below approximately 980 °C.
Figure 10 illustrates the results of analyzing the
structure and composition of the tube material at
the inner surface. An X-ray diffraction pattern
corresponding to the microstructure of Fig. 10(a) is
(c)
Volume 5(4) August 2005 59
 Failure of Ethylene Furnace Outlet Transfer Line Due to Overheating
shown in Fig. 10(b). In addition to the characteristic
reflections of the alloy (Fe-Cr-Ni solid solution, face-
centered cubic structure), characteristic reflections
of the chromium-rich M7C3 and M23C6 carbides
were observed (M stands for metallic elements in
the carbide). Both carbides, however, produced
similar X-ray spectra, as expected. A representative
example is shown in Fig. 10(c). Figure 10(d)
illustrates a spectrum derived from the alloy matrix.
Massive precipitation of carbide phases, as ob-
served in Fig. 9 and 10, is typical of carburization.[4,5]
As demonstrated earlier, under the operating
conditions, the tube alloy developed a nonprotective
surface oxide scale. Thus, carbon deposited on the
surface could readily penetrate the scale and enter
(a) (b)
(c)
Fig. 10 (a) SEM image showing the structure of the tube material. (b) Corresponding X-ray diffraction. (c) EDS spectrum derived from the
matrix and grain-boundary precipitates. (d) EDS spectrum derived from the matrix
60 Volume 5(4) August 2005
(continued)
the alloy substrate, where it reacted with carbide-
forming elements, particularly chromium to form
chromium-rich carbides.
Mode of Failure
Based on the results of this study, it was concluded
that the tube failed by the successive operation of
two fracture mechanisms. At the inner surface,
carburization decreased the ductility of the alloy and
led to brittle intergranular fracture, while the coun-
terweight appeared to impose a state of cyclic stress
that led to fatigue fracture at the outer surface. Car-
burization is known to be a principal cause of failure
in ethylene-cracking furnace components and was
the cause of failure in the system. However, it is
(d)
Journal of Failure Analysis and Prevention
possible that the time to failure was decreased by a
fatigue process that initiated after the intergranular
carburization-induced crack developed in the tube.
Cause of Failure
It is evident from the results obtained that the
failure of the outlet transfer line tube was caused
by overheating as well as adherent coke, which
accelerated carburization at the inner surface, and
the use of a counterweight, which imposed a state
of cyclic stress at the outer surface, leading to
fatigue failure.
Conclusions
It could be concluded from the results of this
investigation that the outlet transfer line tube had
failed by a combination of high-temperature
carburization and fatigue. Although carburization
appeared to be the principal cause of failure, it is
possible that the failure was accelerated by fatigue.
Recommendations
Generally, there are two processes leading to failure
of ethylene-cracking furnace components: creep
damage that is associated with frequent decoking,
and carburization that is associated with less frequent
decoking. In practice, decoking is dictated by process
parameters, particularly gas temperatures, flow rate,
and conversion ratios. However, in such applications
there is every incentive for selecting an alloy highly
resistant to carburization. Most evidence points out
that there is a direct correlation between the
protective nature of the surface oxide scale developed
by a given alloy and its resistance to
carburization.[2,4,8] Alloys that develop Al2O3-base
scale are found to be considerably more resistant to
carburization in comparison with Cr2O3-forming
alloys, such as alloy 800H. It is believed that an
Al2O3-base scale impedes carbon diffusion into the
alloy, which considerably reduces the extent of
carburization.
In view of the results of this investigation, two
recommendations were put forward. First, as a short-
Journal of Failure Analysis and Preven-
tion
term solution, a consideration should be given to
process parameters such as gas temperature, flow rate,
and conversion ratio to better control the deposition
of coke. Because alloy 800H has adequate creep-
rupture strength, a consideration should also be given
to increasing the frequency of decoking. Also, it was
suggested to discontinue the use of a counterweight.
Secondly, for a long-term solution, it was recom-
mended to replace alloy 800H with an Al2O3 -
forming alloy. One of the wrought Al2O3-forming
alloys is the nickel-base Haynes alloy 214 (UNS
N07214). Both alloys 800H and 214 have com-
parable creep-rupture strength; however, alloy 214
is considerably more resistant to carburization, as
determined from carburization tests in reducing
environments resembling those encountered in
ethylene cracking.[2]
Acknowledgment
The authors wish to acknowledge the support of
the Research Institute of King Fahd University of
Petroleum & Minerals.
References
1. J. Blackburn: in “Carburization in High Temperature
Process Plant Materials,” Repon EUR 7773, Colloquium
Proceedings, coordinated by J. Nonon, Commission of the
European Communities, Luxembourg, 1981, p. 7.
2. G.Y. Lai: in High Temperature Corrosion in Energy Systems,
M.F. Rothman, ed., TMS-AIME, Warrendale, PA, 1985,
p. 551.
3. G.M. Smith, D.J. Young, and D.L. Trimm: Oxid. Met.,
1982, 18(5/6), p. 229.
4. H.M. Tawancy and N.M. Abbas: J. Mater. Sci., 1992, 26, p.
1061.
5. A. Schnaas and H.J. Grabk: Oxid. Met., 1978, 12(5), p.
387.
6. M.F. Rothman, G.Y. Lai, M.M. Antony, and A.E. Miller:
Technical File 11622, Haynes International Company,
Kokomo, IN, January 31, 1984.
7. “Incoloy Alloys 800H and 800T Data Brochure,” Inco
Alloys International, Newton, NC, 1986.
8. J. Norton: in “Carburization in High Temperature Process
Plant Materials,” Repon EUR 7773, Colloquium Proceedings,
coordinated by J. Nonon, Commission of the European
Communities, Luxembourg, 1981, p. 43.
Volume 5(4) August 2005 61