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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 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 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 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 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
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
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 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 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
ET 45 Micro).
The performance of this new material was evaluated by comparing the
choking pressure ratio (CPR) of the coil in the 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
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
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
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.
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 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
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 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
HT.
carbides/carbonitrides
Ni-plating
continuous
alumina layer
strong carburization
strong inner
oxidation/spallation
creep voids
carburization
chromium
depletion
inner
oxidation
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