Materials and Corrosion 2003, 54, No.
11 Typical failures in pyrolysis coils
Typical failures in pyrolysis coils for ethylene
cracking
This paper points out the main failure mechanisms for tubes and
outlet parts of pyrolysis furnace coils. In most cases there is a com-
bination of factors which ultimately lead to the failure, e. g. carbur-
ization and creep ductility exhaustion. This results in bulging, bend-
ing and ovalisation of the tubes. Also, brittle fracture during furnace
trips can result in large, longitudinal cracks on many tubes in the
furnace.
The metallurgical background of the combined action of carbur-
ization and creep ductility exhaustion will be explained. Dense and
1 Introduction
Pyrolysis coils in ethylene cracking furnaces are exposed to
very severe conditions, e. g. high temperatures up to 1150 8C,
severe start/stop- and decoke cycles, oxidizing and nitriding
flue gases at the outside and carburizing atmospheres at the
tube inside surface. Therefore, high-alloyed centrifugal cast
Ni-Cr-Fe alloys with adequate high temperature corrosion re-
sistance, good high temperature strength, good machinability
and weldability (even after years of service) are required.
The principle alloys for ethylene cracking furnaces are
shown in Table 1.
In a radiant coil different alloys are being used, each for
specific parts in the coil. Generally speaking, high-carbon
containing alloys are being used inside the firebox, and
low-carbon containing alloys outside the firebox. The highest
Ni-Cr containing alloys are used for the parts with the highest
temperatures.
Radiant coils have a limited life and failure is caused by a
variety of factors, many being related to furnace operation.
However, each pyrolysis plant experiences specific opera-
tional conditions and operational philosophies. Therefore,
each plant has typical causes for radiant coil failure and it
is of importance for operators to analyze and to understand
the typical failure mechanisms. This will enable them to con-
sider the material grades, which would be best suited for those
particular conditions and also to keep failures within limits by
proper furnace operation.
* D. Jakobi
Schmidt þ Clemens Group
Edelstahlwerk Kaiserau, 51779 Lindlar (Germany)
R. Gommans
Gommans Metallurgical Services,
Stevensweert (The Netherlands)
F 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
881
D. Jakobi* and R. Gommans
stable oxide scales on the bore surface lower the amount of catalytic
coke and also the carbon ingress into the alloy matrix (carburiza-
tion). Carburization is also determined by the nickel content of the
matrix. Creep ductility exhaustion is determined by the number of
cycles (start/stop- and decoke cycles) and the nature (or severity) of
these cycles.
Pyrolysis tube failures can be prevented by a combination of
proper furnace operation, materials choice, regular inspections
and good design.
2 Damage mechanisms
2.1 Radiant tubes
The two main failure mechanisms for radiant tubes are :
– ductile failures caused by carburisation and creep ductility
exhaustion;
– and brittle failures caused by thermal shock.
These mechanisms are causing the majority of failures in
radiant tubes.
Other failure mechanisms (such as stretching, overheating,
nitriding, and chromia evaporation) are also described in this
section.
The ductile failure can be recognized by a bulge on the tube
and a short longitudinal crack on top of the bulge (see Fig. 1).
In the micro-structure creep voids can be observed between
matrix and carbides. Further explanation and the metallurgical
background about carburization and ductility exhaustion is gi-
ven in section 3.1.
(front view) (side view)
Fig. 1. Typical ductile failure of a radiant tube in a pyrolysis coil
DOI: 10.1002/maco.200303731
882 Jakobi and Gommans Materials and Corrosion 2003, 54, No. 11

Table 1. Alloys for pyrolysis furnaces

Common SþC Grade C, Cr, Ni, Nb, W, other

Name MärkerÒG/ % % % % %
CentralloyÒCA

HK 40 4848 0.40 25 20 – – Si
– 4868 0.50 30 30 – –
– 4868 Micro 0.50 30 30 – – microalloy
additions
HP Mod Nb 4852 0.40 25 35 1 – –
HP Mod W 4857 W 0.40 25 35 – 4.0 –
HP Micro 4852 Micro 0.45 25 35 1 – microalloy
additions
35/45 Micro ET 45 Micro 0.45 35 45 1 – microalloy
additions
“Alloy 800” 4859 0.10 20 32 1 – –
“HP LC” H 101 0.10 25 35 1.0 – –

in several studies. Investigations and calculations show, that

Fig. 2. Typical brittle failure of a radiant tube in a pyrolysis coil
The brittle fracture can be recognized by a long longitudinal
crack which “ends” in a fork-like appearance (see Fig. 2).
Sometimes, the cracks result in circumferential rupture or
“windows” that fall out of the tube. The cracks can be
many meters long, and many times, a thick coke layer is pre-
sent inside the tube.
In the micro-structure can be observed that the carbides
have split. This is a marked difference to the ductile fracture
and can be recognized easily. Further explanation is given in
section 3.2.
Creep elongation (also called stretching) occurs because of
creep by the self weight of the tube and the coke layer present
in the tube and is influenced by temperature, the load carrying
cross section of the tube, and the material used. It is generally
known that non-carburized HP-micro types creep less than
45Ni/35Cr types. However, carbon uptake (carburization)
leads to a higher specific volume of newly formed carbides
and therefore to internal stresses which cause an increase
in creep rate. The creep elongation of carburized ex-service
centrifugal cast, high carbon tube material has been examined
carburization is a major contributor to longitudinal creep
growth and thus shortening of tube life [1 – 4].
A consequence of a high creep rate is the need to shut down
the furnace and to shorten the coils (some end-users have low-
ered to bottom floor). Failures can occur if tubes are not shor-
tened before they reached the heater floor. The coils are
warped and bowed, resulting in higher tube stresses and creep
rates. There is also a difference of the height of the firebox. In
general, modern higher furnaces suffer more from creep elon-
gation than older smaller furnaces.
Another failure mechanism is overheating, which results in
local melting or overall melting of the tubes. Such an over-
heating can happen due to lack of flow, coke blockage or bur-
ner problems (flame impingement). Lack of flow can occur
when inlet valves fail or in case of compressor problems.
An example of overheated tubes is given in Fig. 3.
Above 1100 8C nitriding respectively internal nitride for-
mation occurs from the outer diameter of the radiant tube
(flue gas side). Nitrogen penetrates through the oxide and re-
acts with chromium by precipitation of nitrides. The precipi-
tation in most cases starts with the conversion of carbides into
carbonitrides M2(C,N), M(C,N) and M6(C,N) which grow by
uptake of chromium and nitrogen [5].
Also, the lack of oxygen in the flue gas plays a role. Under
reducing conditions (many times caused due to flame impin-
gement by badly adjusted burners) this can result in severe
loss of wall thickness by alternating oxidation and nitriding.
The nitrides then cause spallation of the oxides. As a result a
thick layer of oxides (up to 10 – 20 cm (4 – 8 00 ) thick!) can be
found on the furnace floor. Sometimes, this is called oxide
shedding.
Due to nitriding the rough as-cast surface disappears and
the surface becomes a smooth and glazed appearance, see
Fig. 4 a/b.
The changes in materials properties which are caused by
nitriding and carburization are very similar (see section
3.1.). In both cases internal precipitates are formed and the
matrix is more or less depleted of chromium.
Chromia evaporation may become a problem for chromia
forming at high surface temperatures > 1050 8C and high oxy-
gen pressures, as in the flue gases of pyrolysis furnaces.
Materials and Corrosion 2003, 54, No. 11
Fig. 3. Overheating failure of radiant tubes
Fig. 4. a. rough (as-cast) outer surface : typical for new or aged
condition, b. smooth (glazed) outer surface : typical for nitrided
condition
Strong chromium depletion in the alloy subsurface region can
be the consequence and also the formation of a thick carbide
free zone which advances into the alloy. In this area there are
no carbide precipitates for the alloy strengthening available,
and the “sound wall thickness” of the alloy is reduced.
2.2 Bends and outlet parts
Erosion can be observed in 908 or 1808 bends or in Y-pieces,
an example is given in Fig. 5. The most accepted theory is that
erosion is caused by hard coke particles during decoking.
Typical failures in pyrolysis coils 883
Fig. 5. Example of erosion in the cross-section of a 908 outlet bend
(the dashed line depicts the original inner surface)
Fig. 6. Thermal fatigue and curburisation in a return bend of a pyr-
olysis coil (also called “mud cracking” because of its appearance)
Some investigators believe that this erosion is caused by
coke particles, which are present during normal operation.
The remedy is to modify the decoking procedure, so that the
coke is gasified instead of being spalled. Second remedy is to
lower the gas velocity during decoke below 200 m/s. Third
remedy is to apply “internally stepped fittings”, which have
been applied successfully on many occasions.
Thermowells also suffer from erosion by coke particles.
Successful solutions include e. g. thermowells fully made of
Stellite and the rotation of the thermowell at regular intervals.
As in the radiant tubes, carburization also occurs in fittings
(bends, Y-pieces, tetra fittings etc.). In general, such carbur-
ization is not life limiting for the coils, because the radiant
tubes will fail before the fittings do. This is because of the
high wall-thickness of the fittings.
Thick-walled bends and outlet fittings (Y-piece, tetra-fit-
tings, flanges) may suffer from carburization and thermal fa-
tigue. The carburized zone is brittle and already cracks at low
strains. The thermal stresses during start/stop-operation and
decoke cycles cause thermal fatigue at the inside of such
thick-walled components. A distinct feature is that the cracks
are oriented in many directions and are opened widely. Some
people call this “mud cracking” or “crazy cracking” because
of this marked appearance, see Fig. 6. This type of cracking is
not considered to be life limiting of the component.
884 Jakobi and Gommans Materials and Corrosion 2003, 54, No. 11

3 Metallurgical background of the main failure

mechanisms

3.1 Carburization and creep ductility exhaustion

Carburization is an internal carbon enrichment and carbide

formation which occurs mainly in industrial processes where
Cr-Ni-Fe alloys are applied at high temperatures (T > 800 8C)
in carbonaceous atmospheres. The carburisation rate is related
to the carbon activity of the gas (occurs at carbon activities
ac < 1) and progresses exponentially in relation to tempera-
ture [6 – 8].
Carbon pickup increases the metal volume resulting in in-
ternally induced stresses. It progresses from the tube inside
surface causing compressive stresses in the inner wall (carbur- Fig. 7. Inner surface of a tube where the protective oxide scale has
ized tube material) and tensile stresses at the outside (non- failed and carburisation has occurred
carburized tube material). Intergranular cracking results, start-
ing from the middle of the tube wall [6, 7].
Carburization should be negligibly slow at temperatures be-
low 1000 8C for the usual materials with 25% Cr. They form
protective scales composed of an outer spinel layer (Mn, Cr-
oxide) and an inner chromia layer (Cr2O3) which are nearly
impermeable for carbon diffusion from the atmosphere, since
carbon solubility in these oxides is extremely low. However,
there are several mechanisms leading to the failure of the
oxide scale:
l Too large diffusion distance through the de-chromized
zone: The periodic process of chromium oxide growth
and spallation results in a gradual depletion of Cr in the al-
loy subsurface region. A critical thickness of the Cr-de- Fig. 8. Cross-section of a pyrolysis tube with (patchy) carburised
nuded zone is reached in operation at about 200 lm [9, 10] areas
l Conversion of Cr-oxides to non-protective carbide phases
at high temperatures above 1050 8C and high carbon activ-
ities ac > 1. The surface carbides do not provide much pro-
tection against internal carburization [7, 10, 11].
l Structural defects in the protective oxide layer (pores,
cracks, etc.), e. g. cracks formed as a result of thermal cy-
cling [12, 13].
Fig. shows an example of an inner surface of a tube where
the protective oxide scale has failed and carburisation has oc-
curred. Fig. 8 show the cross-section of a pyrolysis tube with
carburised areas. These pictures clearly show the patchy nat-
ure of carburisation, which is caused by local failure of the
oxide scale.
The resistance of materials against carburisation is given by
the Ni-content and the presence of Si, which forms a silica Fig. 9. Pyrolysis tube and deposited coke layer inside the tube. The
sub-scale. Therefore, modern materials have a high Ni content strain range during a decoke cycle is proportional to the temperature
(well above 40%) and Cr contents of minimum 25 – 30% and drop. a-metal
19 lm/mK, a-coke
4 lm/mK, De ¼ Da  DT
contain 1.5 – 2.5% Si. The most modern Cr-oxide forming ma-
terial in this respect is the 45Ni/35Cr-material (such as ET45
Micro) with certain alloying additions (rare earth elements) in does not crush the coke. This causes high tensile stresses in the
order to improve the oxide scale adherence [14]. tube metal, which relax during the (on-line) decoking proce-
Creep ductility exhaustion is a complex mechanism in dure. The strain range that occurs is proportional to the dif-
which the creep ductility is exhausted by cyclic operation ference in thermal expansion coefficient and the temperature
(such as decoke stops, plant shut-downs and trips). During range according to the equation given in Fig. 9.
normal operation a coke layer is deposited at the ID of the During a normal decoke such a temperature drop can be
tube. At the end-of-run (EOR) such coke layers can be up 100 – 200 8C, this causes a strain range of 0.15 – 0.30% which
to 20 mm thick. During the decoking the coke is gasified, corresponds to high stress levels. During the subsequent de-
with the purpose that the tube is clean after the decoke. coking procedure these high stresses relax because of creep.
However, during the change between normal operation and The damage mechanism is thus cyclic creep relaxation. Dur-
decoking a temperature drop occurs. Because the thermal ex- ing each cycle the tube creeps a small amount; and at end-of-
pansion coefficient of the metal is much higher than the coef- life the material reaches its creep ductility. That is were the
ficient of the coke, the metal-tube shrinks on the “coke-tube”. name “creep ductility exhaustion” comes from.
Because of the high compressive strength of coke, the metal Tube life is thus dependent on:
Materials and Corrosion 2003, 54, No. 11
– the number of de-coke cycles (n);
– the severity of the cycle (start/stop, on-line or off-line de-
coke, DT); and
– creep parameters (temperature, material, creep rate, creep
ductility).
The combination of carburisation and creep ductility ex-
haustion is the “normal” failure mechanism for pyrolysis
tubes in ethylene plants. It results in bulges, ovalisation
and sometimes, tube bending as has been described in section
2.1. Each single occurrence is relatively simple to explain, but
the complete process is complex and not yet fully understood.
3.2 Brittle fracture caused by furnace trips
As described in the previous paragraph the metal tube
shrinks on the “coke tube” during a temperature drop. During
a normal decoke the temperature drop is limited to about 100 –
200 8C. During a furnace trip such a temperature drop can be
500 – 1000 8C. The strain during such a furnace trip is then
0.75 – 1.5%. This equals the rupture ductility of aged, carbur-
ized and nitrided material between RT and  600 8C. Since
materials tend to crack when their rupture ductility is reached
... furnace tubes also crack. Because aged, nitrided and car-
burised furnace tube materials are brittle at these tempera-
tures, they crack brittle by splitting the carbides and subse-
quently the tubes. These brittle cracks can extend for many
meters.
The risk for brittle cracks is dependent upon:
– the severity of the trip (temperature drop);
– the thickness of the coke layer inside the tube; thin coke
layers at SOR will be crushed, but thick coke layers at
EOR will not;
– the degree of brittleness of the material, which is deter-
mined by the amounts of ageing and carburization.
As a guideline brittle fracture occurs most frequently when
the tubes are already a few years old and when the furnace is in
the second half of it’s operation run. This “dangerous area” is
given in Fig. 10.
4 Process technological background
The underlying problem for the main failure mechanisms of
radiant tubes is deposition of coke at the ID of the tube. The
coke deposition results in higher tube wall temperatures. For a
tube life of about 6 years in high severity cracking furnaces
Fig. 10. “Dangerous area” for brittle cracking of pyrolysis tubes
Typical failures in pyrolysis coils 885
EOR-temperatures can be up to 1100 8C for HP-materials
(such as G4852 and derivatives) and 1125 8C for 45Ni/
35Cr materials (such as ET 45 micro). At these high tempera-
tures the materials carburize and creep harder.
Therefore, many problems are related to furnace operation.
Overheating, flame impingement, nitriding, oxide shedding,
reducing flue gases, erosion, and especially brittle fracture
can all be prevented by proper furnace operation.
Creep elongation, carburization, and creep ductility ex-
haustion can be kept within limits by proper furnace opera-
tion, proper materials choice and good design.
Furnace inspections may give early detection of up-coming
failures, and should therefore be performed at regular intervals
(e. g. during decoke stops).
It can be helpful to measure carburization. Several compa-
nies offer traditional carburization meters based on magnetic
principles (permeability, eddy current etc.). Recently, Shell
Global Solutions International presented a new pulsed
Eddy Current technique, which showed promising results.
However, a fully carburized tube can have a remnant life
of 1 – 2 years (if no furnace trips occur).
Dimension measurements can be helpful as well. If creep
elongation (stretching) is life limiting for the furnace, it can be
monitored by the position of guide tubes. In most cases creep
in circumferential direction (tube swelling, bulging and ova-
lization) is life limiting. Diameter measurements by simple
strapping can be helpful. However, there will be tubes that
fail at low ductilities (a few percent) and tubes that will
fail at higher ductilities (up to 15% has been observed!).
This is dependent on the way of furnace operation and the
type of material (HK40, HP-Nb or 45Ni/35Cr), but also sig-
nificant scatter between the individual tubes exists.
Accelerated creep testing of ex-service material is not sui-
ted to determine the remnant life of pyrolysis coils, because
the relevant failure mechanisms (combined carburization and
cyclic relaxation) can not be taken into account by a simple
creep test.
For the time being, visual inspections and strapping (dia-
meter measurements) are the best inspection tools. One should
look for bulging, ovalization and appearance (smooth vs.
rough). The results obtained can be used for trending.
Many operators replace tubes about 9 – 12 months after the
first bulges and ovalities are observed.
However, significant developments are being made in mod-
eling the relevant failure mechanisms. Also, statistical ap-
proaches are under development. SþC is developing a statis-
tical method to determine residual coil life based on operating
conditions.
5 Conclusions
l The dominant failure mechanisms for radiant tubes are (a)
the combined action of carburization and creep ductility ex-
haustion, and (b) brittle fracture during furnace trips. The
first mechanism results in bulging, bending and ovalization
of the tubes. The second mechanism results in large, long-
itudinal cracks.
l The metallurgical background of the combined action of
carburization and creep ductility exhaustion are explained.
The carburization rate is determined by the presence of pro-
tective oxide scales, and the nickel and silicon content of
the matrix. Creep ductility exhaustion is determined by
the number of cycles (start/stop- and decoke cycles) and
the nature (or severity) of these cycles.
886 Jakobi and Gommans
l Other mechanisms include creep elongation (stretching),
overheating, nitriding, oxide shedding, thermal fatigue
and erosion.
l Many failures are related to furnace operation and can be
prevented or can be kept within limits by proper furnace
operation, materials choice and good design. Regular fur-
nace inspections may give an early warning of up-coming
failures.
6 Acknowledgements
The authors would like to thank the Schmidt þ Clemens
management for permission to publish this paper.
7 References
[1] V. Guttmann, R. Bürgel, Corrosion and Mechanical Stress at
High Temperatures, Applied Science Publishers, Ltd. London,
1980.
[2] V. Guttmann, K. E. Beck, R. Bürgel, Mat.-wiss. u. Werkstoff-
tech. 1988, 19, 104.
[3] D. E. Hendrix, M. W. Clark, CORROSION/85, paper No. 21,
Houston, TX, NACE International, March 25 – 29, 1985.
Materials and Corrosion 2003, 54, No. 11
[4] D. E. Hendrix, CORROSION/98, paper No. 430, Houston/TX
USA, NACE International, 1998.
[5] I. Aydin, H. E. Bühler, A. Rahmel, Werkstoffe und Korrosion
1980, 31, 675.
[6] D. L. Bagnoli, J. J. Krupowicz, CORROSION/92, paper No.
307, NACE International, Houston 1992.
[7] H. J. Grabke, Carburization – A high Temperature Corrosion
Phenomenon, MTI Publications No. 52, St. Louis, Elsevier
Science, Amsterdam, New York 1998.
[8] H. J. Grabke, Materials at high temperatures 2000, 17, 483.
[9] R. Petkovic-Luton, T. Ramanarayanan, Oxidation of Metals,
1990, 34 381.
[10] T. A. Ramanarayanan, R. A. Petrovic, J. D. Mumford, A.
Ozekcin, Materials and Corrosion 1998, 49 226.
[11] H. J. Grabke, U. Gravenhorst, W. Steinkusch, Werkstoffe und
Korrosion 1976, 27, 291.
[12] I. Wolf, H. J. Grabke, Solid State Comm. 1985, 54 5.
[13] I. Wolf, H. J. Grabke, H. P. Schmidt, Oxidation of Metals,
1988, 29, 289.
[14] R. Kirchheiner, J. L. Jimenez, CORROSION/2001, paper No.
01374, Nace Conference, Houston/TX, USA, NACE Interna-
tional, 2001.
(Received: June 4, 2003) W 3731