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AI ChE Paper Number 88b

ADVANCED MATERIALS FOR RADIANT COILS




Dr. Dietlinde J akobi
Schmidt + Clemens GmbH + Co. KG
51789 LINDLAR/GERMANY


Dr. J rg Weigandt
Schmidt + Clemens GmbH + Co. KG
51789 LINDLAR/GERMANY


Prepared for Presentation at the 2010 Spring National Meeting
San Antonio, Texas, March, 22 25, 2010


AIChE and EPC shall not be responsible for statements or opinions contained in
papers or printed in its publications

ADVANCED MATERIALS FOR RADIANT COILS
Dr. Dietlinde J akobi
Schmidt + Clemens GmbH + Co. KG, 51789 LINDLAR/GERMANY
Dr. J rg Weigandt
Schmidt + Clemens GmbH + Co. KG, 51789 LINDLAR/GERMANY


Abstract


Because radiant coils operate under severe conditions of carburization,
oxidation and creep, tube material selection plays an important role.
The Schmidt + Clemens bench-scale unit allows simulation of the
possibility to simulate high temperature corrosion of alloys in petrochemical
plants: samples are examined at steam cracking conditions, i.e. high metal
temperatures/ lower gas temperatures, low residence times in order to provide
catalytic and pyrolytic coke formation (similar to the coke formed in the radiant
coils) and a gas mixture which corresponds to the composition within the outlet
tube of a radiant coil.
This new and unique high temperature corrosion test rig allows S+C to
improve and develop centrifugal cast materials for radiant coils in a very fast and
focused way. Therefore, the tube materials can be "tailor- made in accordance
with the customer's needs, the specific coil design, operating conditions and feed
contaminants.
Exemplary test results of a new class of the alumina forming materials
the "HT-Alloys family and also the results of field applications will be presented:
Despite the excellent combination of a high carburization & oxidation resistance
and excellent creep strength the alloy Centralloy

HT E was further refined for
steam cracker applications by optimizing the oxide layer stability and reducing
the catalytic coke formation.
Introduction


Thermal cracking of hydrocarbons in the presence of steam is the main
process for the production of the lower olefins, ethylene and propylene.
It proceeds in pyrolysis heaters by feeding the hydrocarbon/steam mixture
into tubular reactor coils which are fired by bottom and/or wall burners in a
firebox. Such radiant coils are exposed to very severe conditions: high metal
temperatures and alternating corrosive atmospheres combined with cyclic tensile
stresses; therefore coil materials exhibit a limited and non-predictable lifespan.
In the course of the cracking process, tube metal temperatures increase
as a consequence of coke formation which develops on the inner tube surface.
Coke is deposited mainly according to two different mechanisms: catalytic coke
(filamentous coke) and pyrolytic coke (1,2,3) Catalytic coke is formed at catalytic
active sites on the coil material surface: for instance an active metal particle may
be lifted from the tube surface and acts as a catalyst for coke growth to form
thin filaments. This type of coke is only formed in the first hours or days after
the hydrocarbons are added to the pre-oxidized radiant coils (during the furnace
start-up), but it is very important, as it causes a fast initial decrease of the heat
transfer when deposited on the surface. Pyrolytic coke is formed as a function of
the feed composition and the operational parameters (e.g. cracking severity). It
is continuously formed during the thermal cracking of hydrocarbons. The
insulation effect of this growing coke layer leads also to a gradually increasing
pressure drop, which impacts on the product selectivity (ethylene and
propylene). The reduced heat transfer is compensated by a gradual increase in
heat output of the burners, resulting in an increased tube metal temperature.
When the maximum allowable operational parameters are reached (e.g. upper
limit in tube metal temperature), a so called "decoking operation is performed
by using an air/steam mixture: the coke is burned off in an exothermic reaction.
This time consuming process results in a significant loss of production.
Preventing or retarding coke formation and prolonging the cracking run
length as well as the lifetime of tubes by any reasonable measures have an
enormous economic advantage. From the reasons mentioned above it is
apparent that the metal quality and the pretreatment of the radiant coils during
the furnace start-up (formation of a dense, continuous, defect-free oxide layer)
is extremely important.
Material Development for Radiant Coils


The upper temperature limit for radiant coils is determined by the coil
material properties: highly alloyed centrifugally cast materials are required with
adequate creep strength and structural stability at high operating temperatures.
Additionally, these alloys must possess excellent oxidation, carburization and
coking resistance (4,5,6).
The maximum tube metal temperature of alloys presently used in ethylene
cracking furnaces is 1150C and the aim is to achieve even higher operating
temperatures. Therefore, Schmidt + Clemens has developed a new class of
alumina forming materials the Centralloy

HT Alloy Family.
Aluminum additions above a certain level lead to the formation of a
thermodynamically very stable alumina layer this is much more stable than the
chromium oxides formed on the surface of standard materials. Under typical
cracking conditions, the chromia layer converts to carbides if heated to
temperatures above 1050C and as a consequence the shielding and protective
effects of chromium oxides are completely lost in due time (7). Alumina on the
other hand does not convert to carbides and keeps its protective properties for
the lifetime of the base material.
The dense, strongly adherent aluminum oxide layer formed on the surface
of the Centralloy

HT alloys therefore offers excellent protection against attack


by oxidation and carburization at temperatures beyond 1150C. Moreover, it
significantly reduces the formation of catalytic coke in carbon rich steam cracking
atmospheres. All Centralloy

HT modifications exhibit an excellent structural


stability, a very good creep resistance and high temperature creep rupture
strength. The alumina forming material Centralloy

HT possesses - compared to
standard chromia forming alloys - superior resistance to cyclic oxidation at high
temperatures (1150C) and has therefore the ability to be rehealed in service
during decoking. Figure 1 presents the typical weight loss of metal samples
(oxide loss at the surface) as a function of the number of cycles for standard
chromia forming materials as well as for the alumina forming Centralloy

HT
material at 1150C testing temperature. The standard alloys suffer after a few
cycles from high weight loss (spallation of oxide at the surface) and the
Centralloy

HT alloys reflect a parabolic aluminum oxide scale growth rate and


no further change in weight over 250 cycles (no spallation).
The state-of-the-art alloys for ethylene coils are shown in Table 1.
Depending on the furnace design and the specific operating parameters, the coil
consists of one or several materials: lower grade alloys (e.g. 25Cr/20Ni to
25Cr/35Ni alloys) in the colder passes and higher grade alloys (e.g. 35Cr/45Ni
and aluminum containing HT alloys) in the hotter passes, as these areas of the
coil suffer more from corrosive attack and coking.
The Centralloy

HT materials used for the hottest (outlet) passes of the


ethylene cracking coils are produced as spun cast tubes, but also as induction
bent tubular components or statically cast fittings (return bends, elbows, y-
pieces).
The welding procedures are available for matching but also for all
dissimilar weld joints to standard austenitic materials. The welding of aged
materials has been studied on tube sections removed from different field
applications after several years in service and therefore also repair welding
procedures can be supplied on request.


New Strategies for Radiant Coil Material Development:
Tailor Made Materials


Conventionally, tube material development is carried out by testing
different alloy compositions separately with respect to specific alloy properties:
e.g. creep rupture tests are performed in order to evaluate the creep rate and
creep strength (time to rupture), pack carburization or gas phase carburization
tests are performed to simulate the carbon diffusion into the alloys matrix and
cyclical oxidation tests are carried out to evaluate the stability of oxide layers and
its adherence to the base material (8,9). But it is difficult to simulate coke
formation and the interaction with the tube material on a laboratory scale in the
same way as it occurs in commercial cracking tubes (10,11,12,13).
Therefore, a new approach was used to build an unique test rig dedicated
to simulate and investigate the gas-surface interaction at the radiant coil outlet
of a steam cracker where the tube material is exposed to the most severe
conditions regarding temperature and reactive gas. The effect of different
operating conditions can be studied in this test rig: e. g. the pre-conditioning of
the alloys, the start-up of new and aged coils, as well as the cracking of
hydrocarbons and the resulting coke formation as well as subsequent decoking.
All of these factors may be studied separately or consecutively in this way. Also,
several gases can be mixed in a wide range of compositions and reactive
elements and/or feed impurities can be added to the process gas. Other key
features of the actual process parameters in an industrial cracking furnace have
been implemented in the test rig, e.g. the gas-residence time and the
temperature of the gas combined with a typically higher sample temperature.
This setup therefore effectively simulates the relevant process steps of a steam
cracker in a very realistic way (14).
The advantage of this testing procedure is that samples can be taken off
from the rig at any stage of a simulated cracker operation, e. g. after the start-
up of the furnace (pre-oxidation) or after a certain number of cracking/decoking
cycles, in order to study the coking behavior and the relevant chemical and
structural changes of the tube material.
The test rig therefore allows therefore a structured examination to qualify
modified or newly developed alloys for radiant coils. Furthermore it enables
testing of new or optimized process conditions in terms of their benefits in
achieving better cracking furnace performance or better resistance of the tube
materials against coking, corrosion and carburization (14).
As a result of the alumina forming material family Centralloy

HT could be
further refined by optimizing the diffusivity of oxide forming elements in the
matrix. It could be demonstrated that the faster diffusion of oxide forming
elements stabilizes the initially formed oxide scale (grown during the furnace
start-up) with respect to catalytic coking and, during the normal cracking
process, with respect to high-temperature corrosion resistance. It has also been
shown that the aluminum content needs to be well above a certain level (3%) in
order to form a uniform and dense protective alumina scale.
Different Centralloy

HT alloy modifications were tested in the S+C test
rig under cyclic operating conditions corresponding to those in an ethylene
cracking furnace. Some modifications turned out to have a very different
resistance to the oxidizing and carburizing atmosphere: e.g. the alloy
modification Centralloy

HT A suffered after only three cycles from detrimental


changes.
Considerable amounts of Al
2
O
3
formed at interfaces and grew into the
near-surface areas of the base material (inner oxidation at phase-, grain- and
subgrain boundaries). Only a small surface fraction remained covered by alumina
and non-uniformly grown chromia nodules were present on the surface. Small
parts of the matrix are encapsulated by oxides. These "islands are depleted in Al
and Cr which increases their Ni-fraction and thus, potential catalytic sites for
coke formation have been created at the surface (as Ni is highly catalytically
active). After 10 cycles the situation became worse (Figure 2). The inner
oxidation penetrated deeper, the chromia nodules were more pronounced and
the quantity of Ni-rich metal islands in the surface increased.
In both experiments (3, 10 cycles) of alloy Centralloy

HT A carburization
was visible in the subsurface area. This produced a higher density of small
carbides in the matrix. The carburization mainly occurred due to the lack of a
dense, continuous protecting oxide layer. The matrix of the base material itself
actually should at least be as resistant as alloy Centralloy

HT E against
carburization which besides the existence of a protecting oxide as diffusion
barrier is also controlled by the solubility and by the diffusivity of carbon in the
matrix material.
After 10 cycles the alloy Centralloy

HT E maintained a dense alumina


layer covering the entire sample surface (Figure 3). Normally, carbide
precipitation within the alloy's matrix provides an excellent creep strength, but if
present at the tube surface, these carbides might interrupt the continuous oxide
scale or lead to the formation of a different oxide layer composition which can
contain catalytically active sites. Therefore, it is absolutely essential to form
initially (during the start-up of a new coil) a dense and catalytically non-active
oxide layer. After exposure of the alloy Centralloy

HT E to 10 cracking &
decoking cycles the carbides were still covered by alumina, others were
encapsulated by alumina. No spalling, cracking of the oxide layer and no inner
oxidation of the base material could be observed. Ni-rich metallic particles were
not observed on the surface of this material Centralloy

HT E.
The structure of the oxide layer corresponds to an -alumina type of
oxide. This continuous and dense oxide layer protected the base material of the
alloy Centralloy

HT E from carburization.
Figure 2 and Figure 3 show the extent of the Al-depletion in the base
material near the oxide layer, analyzed by EPMA. The alloy Centralloy

HT E with
the continuous alumina layer is not depleted in aluminum, which in the long term
is an important prerequisite for the material to maintain or to regenerate a stable
alumina layer. Due to the considerable degree of inner oxidation alloy
Centralloy

HT A exhibits a near-surface zone in which Al is depleted. In the area


with inner oxidation the aluminum concentration tends to zero (Local fluctuations
in the profiles are caused by small carbide precipitates).
This means that after several cycles in operation, the protective alumina
scale formed initially on the surface of the alloy modification Centralloy

HT A
can not be regenerated and the surface contains catalytically active sites (high in
Ni content) while the state of the art modification Centralloy

HT E is still
perfectly protected by an alumina scale and does not suffer from any aluminum
depletion.
In addition to the above mentioned development of new alloys and
refining of existing materials, the test rig enables S+C to provide process
recommendations in order to achieve a better cracking furnace performance:
e.g. longer run lengths (due to reduced catalytic coke formation), shorter
decoking times, increased conversion rate or increased furnace capacity or
longer cracking coil life.
The excellent behavior of alumina forming S+C Centralloy

HT materials
has been confirmed in a large number of field applications with the first
generations of the Centralloy

HT material (e.g. alloy Centralloy

60HT E) as
well as the optimized state of the art alloy Centralloy

HT E.

Status and Experience with Alumina Forming Alloys -
Centralloy

HT Family


The first coils in Centralloy

HT material have been installed in


Petrochemical Industry furnaces in 2003 followed by a wide range of partial and
full furnace applications both in gas as well as in naphtha cracking furnaces:

- Kellogg Millisecond (gas cracker)
- Technip / KTI (gas cracker)
- Several Linde Pyrocrack 1-1 (naphtha cracker)
- Linde Pyrocrack 1-1 (gas cracker)
- Several Linde Pyrocrack 4-2 (naphtha cracker)
- Linde Pyrocrack 4-2 (gas cracker)
- Linde LSCC 4-2 (naphtha cracker)
- Several Linde Pyrocrack 2-2 (naphtha cracker)
- Several Linde Pyrocrack 2-2 (gas cracker)
- Two Lummus SRT V (naphtha cracker)
- Lummus SRT V (gas cracker)
- Several KTI multiple pass (naphtha cracker)
- KTI 4 pass (gas cracker)
- Stone & Webster 24W (gas cracker)

The benefits of the application of improved Centralloy

HT furnace tubes
have been realized in different ways: by increasing the run length, by utilizing
the higher temperature stability of the alumina forming material to allow an
increase in furnace severity and thus e.g. increasing the ethylene conversion rate
(with maintained run length), by increasing the furnace capacity or simply by
increasing the tube/coil life.
All these applications with Centralloy

HT materials enabled S+C to collect


furnace data and experience for more than 7 years up to now.

One of the first modifications of the alumina forming Centralloy

HT alloy
family has been applied in October 2003 in a Linde Pyrocrack 1-1 furnace of the
Braskem UNIB-RS plant. Tubes, bent tubes as well as fittings in Centralloy


60HT E material have been installed in this furnace operated with a rather high
cracking severity. With this new Centralloy

60HT E material, the runtime of the


furnace was significantly increased under the same furnace settings as before.
Exemplary field test results:

Short Residence Time Gas Cracker

The Centralloy

HT material has been installed in 2005 in one coil (consisting of


24 tubes) of a Linde Pyrocrack 1-1 furnace, all other coils of this furnace have
been equipped with the standard chromia forming 35Cr/45Ni-alloy (Centralloy


ET 45 Micro).
The performance of this new material was evaluated by comparing the
choking pressure ratio (CPR) of the coil in the Centralloy

HT material to the CPR


of the coils equipped in the 35Cr/45Ni material. In these furnaces EOR (End of
Run) is generally determined by the CPR. The CPR increase for the coils
equipped with the standard material (Centralloy

ET 45 Micro) has been


evaluated in comparison with the Centralloy

HT material: the average CPR


increase in time for the Centralloy

HT material was less than half of the CPR


increase in time for the standard material Centralloy

ET 45 Micro (35Cr/45Ni-
alloy). It can therefore be concluded that coke lay-down in the Centralloy

HT
coil is much less owing to the formation of a continuous and stable alumina layer
in that coil as compared to the other coils. It has also been demonstrated that
the material possesses an excellent thermal stability.
On the basis of these results the customer may increase the ethylene yield
(higher severity) of a furnace fully equipped with the alumina forming
Centralloy

HT material in case the run length is kept constant (owing to the


lower amount of coke formation). If on the other hand the run length should be
more important the run length of a furnace equipped with this alumina forming
material could be more than doubled.
Run length prolongation in this case gives savings of around 150,000
per year from less decokings alone, while at the same time the increase of
furnace availability amounts to approx. 6,000 tons (~6%) of ethylene per year
(being an equivalent to 1,2 Mio per year).

Naphtha Cracker

In 2004, a Linde Pyrocrack 1-1 furnace was recoiled with tubes made of the
alumina forming material Centralloy

HT replacing the standard material


Centralloy

ET 45 Micro (35Cr/45Ni). Process data of this furnace were


compared by statistical means (S+C- RCLP multiple regression analysis program)
with similar Linde Pyrocrack 1-1 furnaces equipped with the 35Cr/45Ni material
(operated under the same process conditions).
The furnace equipped with Centralloy

HT material consistently showed a


more than double run length compared to the furnaces with Centralloy

ET 45
Micro (35Cr/45Ni) coils over more than 5 years. Moreover, an increase of the
overall furnace availability was experienced owing to less decokings and less
maintenance work. As a result the production of ethylene equivalents could be
increased by 2,700 tons per year (a yearly production increase of 6%) in this
recoiled furnace alone resulting in an average profit of 540.000 per year.

Gas Cracker: Metallurgical evaluations preformed after 3 years in
operation

Several tube sections have been removed by an end-user from different Linde
Pyrocrack 2-2 furnaces which have been operated with gas feed over 3 years
at the same furnace settings.
Metallurgical evaluations have been performed in order to compare the
behavior of the standard materials 25Cr/35Ni (Centralloy

4852 Micro) and
35Cr/45Ni (Centralloy

ET 45 Micro) with the performance of the Centralloy

HT
alloy exposed to the same conditions in the hottest outlet passes of these
cracking furnaces.
Figure 4 shows the corrosive attack which occurred on the inner tube surface
of the three different materials:
The investigations revealed that the lowest alloyed material, the 25cr/35Ni
alloy (Centralloy

4852 Micro), was strongly carburized (carbon contents up to


max. 4%), strong corrosive attack occurred on the inner tube surface leading to
spallation of the protective oxide layer. The chromium content in the sub-surface
area was reduced below a critical level due to formation of chromium carbides
(carburization); therefore the protective oxide scale could not be regenerated
during the normal de-coking process. The high amount of catalytically active
sites on the inner surface (mainly Ni particles) caused a faster catalytic coke
formation which shortened the furnace run-length. This higher number of de-
coking cycles and the carburization of the tube material caused a significant
reduction of the creep strength (creep voids have been detected in the alloys
matrix) leading to the reduction of the tube life.
The highest grade standard material 35Cr/45Ni, the Centralloy

ET 45 Micro,
was also carburized (max. carbon content 1.6%), inner oxidation occurred as
well as spallation of the oxide layer, but no creep damage has been detected in
the tube sections removed from service.
Exposed to the same strongly reducing conditions in the outlet passes of the
Linde Pyrocrack 2-2 furnace, the Centralloy

HT material showed after 3


years in operation still a continuous protective alumina layer, the material was
not carburized and the furnace consistently showed higher (double) run-lengths.
These results confirmed the superior stability of the alumina layer formed on
the inner surface of radiant coils equipped with the material Centralloy

HT.


Conclusions

Radiant coils for cracking furnaces operate under severe cyclic conditions
of carburization, oxidation and creep, and therefore material selection plays an
important role. The unique S+C high temperature corrosion test rig offers the
ability to improve and develop spun cast materials for radiant coils and to test
furnace specific operational settings in a very fast and well focused way. Tube
materials can be "tailor-made depending on customer needs, the specific coil
design, operating conditions and feed contaminants.
This test rig has been operated over several years with a large number of
results regarding material composition, surface quality, material pre-treatment
during the furnace start-up with new coils or after de-coking and material
deterioration during the normal cracking process.
As a result the alumina forming family of Centralloy

HT-alloys has been


further refined by optimizing the diffusivity of oxide forming elements in the
matrix. By this means the initially formed oxide layer was stabilized with respect
to catalytic coking and to high-temperature corrosion resistance. Also, the
tendency to suffer severe inner oxidation has been reduced drastically.
Therefore, the state of the art material, the Centralloy

HT E, provides
excellent creep strength, excellent carburization and oxidation resistance and
higher temperature stability together with a substantially reduced coking rate
compared to conventional alloys.
The Centralloy

HT materials have been in operation since the year 2003


in a number of different furnace designs in gas as well as in naphtha crackers.
The benefits have been realized in different ways: by longer (e.g. doubled) run-
lengths or shorter decoke times (when operational parameters are maintained)
resulting in increased furnace availability, increased conversion rates or increased
furnace capacity or simply in an increased coil life.



-10
0
10
0 50 100 150 200 250
Number of Cycles
W
e
i
g
h
t

C
h
a
n
g
e
,

m
g
/
c
m

Centralloy G 4852 Micro


Centralloy ET 45 Micro
Centralloy HT E
Tables

Table 1: State of the art alloys for pyrolysis furnace coils

S+C Grade
Centralloy


C
(%)
Cr
(%)
Ni
(%)
Nb
(%)
Fe
(%)
Al
(%)
Additions,
other
G 4848 0.4 25 20 - bal. - -
G 4868 0.5 30 30 - bal. - -
G 4868 Micro 0.5 30 30 1 bal. - MAE, RE
G 4852 0.4 25 35 1 bal. - -
G 4852 Micro 0.4 25 35 1 bal. - MAE, RE
ET 45 Micro 0.4 35 45 1 bal. - MAE, RE
HT Alloys 0.4 24-33 bal. 1 15-25 3.0-6.0 W, MAE, RE
RE: Addition of reactive elements; MAE: Addition of micro-alloying elements



Figures



Figure 1: Cyclic oxidation of metal samples, comparison: chromia forming
standard alloys and alumina forming alloy Centralloy

HT E (45 min at 1150C,


15 min at room temperature in air)



0,0
0,2
0,4
0,6
0,8
1,0
1,2
0 20 40 60 80 100
depth [m]
n
o
r
m
a
l
i
s
e
d

c
o
n
c
e
n
t
r
a
t
i
o
n


Figure 2: (a), (b) Alloy Centralloy

HT A: oxide layer and structure at the inner
surface of a tube after 10 coking / decoking cycles
(c) Normalized concentration profile of aluminum near the inner tube wall after
10 coking / decoking cycles at 950 C
M
23
C
6
inner oxidation

(a)
Cr
2
O
3
(b)
Al
2
O
3
Ni-rich
(c)
Centralloy

HT A
Aluminum profile
Carbide precipitates


0,0
0,2
0,4
0,6
0,8
1,0
1,2
0 20 40 60 80 100
depth [m]
n
o
r
m
a
l
i
s
e
d

c
o
n
c
e
n
t
r
a
t
i
o
n

Figure 3: (a), (b) Alloy Centralloy

HT E: oxide layer and structure at the inner
surface of a tube after 10 coking / decoking cycles at 950 C
(c) Normalized concentration profile of aluminum near the inner tube wall after
10 coking / decoking cycles at 950C
Al
2
O
3
scale
(a)
M
23
C
6

covered by Al
2
O
3
(b)
(c)
Aluminum profile
Carbide precipitates
Centralloy

HT E

(a)
(b)


(c)


Figure 4: Metallurgical evaluations after 3 years in operation in the outlet
passes of a Linde Pyrocrack 2-2 gas cracker: (a) alloy Centralloy

4852 Micro,
(b) alloy Centralloy

ET 45 Micro and (c) alloy Centralloy

HT.

carbides/carbonitrides
Ni-plating
continuous
alumina layer
strong carburization
strong inner
oxidation/spallation
creep voids
carburization
chromium
depletion
inner
oxidation
References

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hydrocarbons", Review in Chemical Engineering 6 No. 4, 293-328
2. L. Albright, J . Marek (1988), "Analysis of Coke Produced in Ethylene
Furnaces, Insights on Process Improvement", Industrial & Engineering
Chemistry Research 27 No. 5 , 751-755
3. L. Albright, J . Marek (1988),"Mechanistic Model for Formation of Coke in
Pyrolysis Units Producing Ethylene", Industrial & Engineering Chemistry
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4. D.J . Tillack, J .E. Guthrie (Feb. 1998), "Wrought and Cast heat resistant
stainless steels and nickel alloys for the refining and petrochemical
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5. S. B. Parks, C.M. Schillmller(1997), "Use these alloys to improve ethylene
production, Stainless Steel World 9, 27-35
6. D.R.G. Mitchell, D.J . Young, W. Kleemann (1998), "Carburisation of heat-
resistant steels, Materials and Corrosion 49, 231-236
7. D. J akobi, R. Gommans (2003), "Typical failures in pyrolysis coils for
ethylene cracking, Materials and Corrosion 54, 881 887
8. D.J . Tillack, J .E. Guthrie (Feb. 1998), "Wrought and Cast heat resistant
stainless steels and nickel alloys for the refining and petrochemical
industries, Nickel Development Institute Technical Series 10071
9. S. B. Parks, C.M. Schillmller (1997), Use these alloys to improve ethylene
production, Stainless Steel World 9, 27-35
10. G. F. Froment, K.M. Sundaram (1979), "Kinetics of Coke Deposition in the
Thermal Cracking of Propane, Chemical Eng. Science 34, 635-644
11. L. Albright, J . Marek (1988), "Coke Formation during Pyrolysis:Roles of
Residence Time, Reactor Geometry, and Time in Operation, Industrial &
Engineering Chemistry Research 27, 743-751
12. G. Zimmermann, W. Zychlinski, B. Ondruschka, H. Woerde, P. van den
Oosterkamp (1997), "Studies in a new ring cracking reactor with radial
temperature gradient, Chem.-Ing.-Tech. 69, 662-666
13. G. Zimmermann, W. Zychlinski, H. Woerde, P. van den Oosterkamp
(1998), "New developments in fouling inhibition of cracking coils and
TLE's, 10th Ethylene Producers Conference, 189-203
14. D. J akobi, C. van de Moesdijk, P. Karduck, A. von Richthofen (2009),
"Tailor Made Materials for High Temperature Applications: New
Strategies for Radiant Coil Material Development, NACE Corrosion 2009,
Paper No. 09155.

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