Experiences of HP-Nb&Ti Catalyst
Tubes after Using of Long Term at
Elevated Temperature
Toshikazu Shibasaki, Takaaki Mohri and Ikuo Kojima
Chiyoda Corporation, Yokohama, Japan
Introduction
HP-Nb&Ti (25Cr-35Ni-Nb-Ti-0.45C Iron Base
Heat Resisting Cast Alloy) has been applied to catalyst
tubes since 1985. There are some advantages to using it
for catalyst tube material1). The superior creep rupture
strength relative to HK40 (25Cr-20Ni-0.4C Iron Base
Heat Resisting Cast Alloy) or IN519 (24Cr-24Ni-0.3C-
Nb Iron Base Heat Resisting Cast Alloy) is one advan-
tage. We describe some experiences with HP-Nb&Ti
materials for catalyst tubes after long term use at ele-
vated temperature. Then we propose a method to main-
tain the catalyst tubes. In order to estimate the remain-
ing tube life by measuring the change of inner
diameter, the behavior of tube deformation with
creep should be clarified. The relationship be-
tween the deformation and the age of the catalyst
tube material is provided by the constitutive creep
equation. The modified theta concept is used to
present the creep behavior2).
Situation of Application for HP-Nb&Ti
Catalyst Tubes
Figure 1 shows the change of materials for catalyst
tubes in Chiyoda Corporation. In 1965, HK40 material
was selected for catalyst tubes. However, due to the
lower creep rupture strength and the lower ductility af-
ter use at high temperature, HK40 was replaced by
2004
IN519 material after 1975. Subsequently, the desire for
higher operating temperature of the catalyst tubes was
required even higher creep rupture strength than IN519.
In 1985, HP-Nb&Ti material was begun to be applied
for catalyst tubes. At this point in time, more than half
of the total numberｓ of catalyst tubes, installed by
Chiyoda Corporation, are HP-Nb&Ti materials.
Some HP-Nb&Ti catalyst tubes were sampled from
the furnace to assess the remaining tube life in that fur-
nace. Figure 2 shows the state of remaining life assess-
ment of catalyst tube in the furnace whose tubes were
installed by Chiyoda Corporation. There are two ways
to assess the tube remaining life. One is destructive ex-
amination, which is notated in the figure as “E”, for the
tube sampled from the furnace. The other is non-
destructive examination, which is notated in the figure
as “N”, for all of the tubes or half of the tubes in the
furnace. The first way is more reliable but the number
of tubes examined is small. The second way is a faster
way to evaluate the remaining life and all of the tubes
can be examined. We describe the results of destructive
examination at Plant A and Plant C after 13 years ser-
vice and 12 years service respectively.
41 AMMONIA TECHNICAL MANUAL
Change of Metallurgical Properties After
Using
HP-Nb&Ti materials were developed based on the
HP-Nb materials are being modified by the method of
micro-alloying. In this case, Ti is the important element
used to improve the metallurgical properties, especially,
the stability of precipitates. The growth rate of Nb - Ti -
carbides is slow than that of Nb – carbides under high
temperature condition, and the high temperature
strength, especially creep rupture strength, is main-
tained at a high level.
Photograph 1 shows the microstructures of HP-
Nb&Ti materials before aging and after aging at lower
temperature, which corresponds to the upper portion of
a catalyst tube in the steam reformer furnace, and at
higher temperature, which corresponds to the maximum
tube skin temperature portion of the tube, after 12 years
of service in Plant C. To compare the change of micro-
structures between HP-Nb&Ti (adding Nb and Ti alloy-
ing elements) and IN519 (adding only Nb element) ma-
terials, the microstructures of IN519 materials after
aging under nearly identical conditions of HP-Nb&Ti
materials as shown in Photograph 1, are presented in
Photograph 2.
The shape of primary carbides is nearly maintained
in as cast condition. The number of secondary carbides
per unit area in HP-Nb&Ti material is much greater
than that of IN519 materials.
Figure 3 and Figure 4 show the distribution of
Vickers Hardness (Hv) along the tube length of HP-
Nb&Ti and IN519 materials after use in Plant A and
Plant U respectively. The service period of the catalyst
tubes shown in Figures 3 and 4 is approximately the
same. However, the minimum Hv of the IN519 tube is
lower than that of the HP-Nb&Ti tube. This corre-
sponds to the change of microstructure described above.
Figure 5 and Figure 6 show the result of tension
testing of HP-Nb&Ti materials after operating for 6 and
13 years in Plant A. The change of tensile strength is
small, close to the initial condition. However, the ten-
sile ductility at ambient temperature decreases after ag-
ing. This corresponds to the changes of microstructure
and Hv after the aging described above. On the other
hand, the tensile ductility at high temperature is nearly
the same as the initial conditions as shown in Figure 7
which presents the tensile ductility versus temperature
AMMONIA TECHNICAL MANUAL
of an HP-Nb&Ti catalyst tube after use in Plant C for
12 years.
Change of Creep Rupture Strength After
Using
In the destructive examination of a sample catalyst
tubes, we performed a creep tests to evaluate the re-
maining life quantitatively and to estimate the relation-
ship between the creep deformation and the tube life
consumption.
Figure 8 and Figure 9 present creep rupture strength
master curve of used HP-Nb&Ti materials sampled
from the maximum skin temperature portion of a cata-
lyst tube in Plant C and Plant A after 12 and 13 years
respectively. However, those curves are estimated
based on the short period creep tests, 100 hours to
2,000 hours. Therefore, note that the results are only for
reference, but are useful to estimate within short period
of the future, 20,000 and 30,000 hours. Figure 10 and
Figure 11 show the result of testing temperature versus
rupture time for used HP-Nb&Ti materials in Plant C
and Plant A calculated from the creep rupture strength
master curves shown in Figures 8 and 9. The applied
stress for those catalyst tubes appears to be 1.3 to 1.9
kg/mm2 (about 13 to 19 MPa), which is caused by in-
ternal pressure and the residual thermal stress due to the
temperature gradient between the inside and outside of
the tube. The maximum tube skin temperature of those
catalyst tubes is estimated at 880 to 920 degrees C
(about 1,173 to 1,213 K) based on the change of micro-
structures.
With the above applied stress and the tube skin
temperature, both materials sampled from Plant C and
Plant A after being service for 12 and 13 years respec-
tively have maintained high creep rupture strength. Fig-
ure 12 shows the result of testing temperature versus
rupture time for used IN519, which are presented by
dark notations, and HP-Nb&Ti, which are presented by
clear notations, after use for nearly same period, 12
years, and nearly same operating condition in order to
compare the creep rupture strength. It is confirmed that
the creep rupture strength of used HP-Nb&Ti material
under normal condition of catalyst tube in the actual
furnace maintains high strength to continue the opera-
tion.
42 2004
Maintain the Catalyst Tubes
It is useful to measure the change of dimension es-
pecially the inner diameter (hereinafter called ID) of
catalyst tube to evaluate the remaining life of HP-
Nb&Ti as with IN519 catalyst tubes3). Figure 13 is the
result of measurement of ID after HP-Nb&Ti catalyst
tube in Plant C in service for 12 years. The tube skin
temperature becomes higher near the bottom of the
tube. The maximum change of ID corresponds to the
maximum tube skin temperature portion. In this case,
the maximum change of ID is less than 1%; therefore,
the remaining tube life seems to be more than 50,000
hours.
Constitutive Creep Equation of Modified
Theta Concept
The constitutive creep equation of modified theta
concept4) is described in equation (1). The constants and
the coefficients in the equation are presented in equa-
tion (2) to (5). Constants A, B, α and ε 0 in equation
(1) are given as a function of normalized stress (σ/E)
and temperature (T).
ε=ε0 +A(1–exp(-αt))+B(exp(αt)-1) (1)
ε : creep strain
t : time
ε 0, A, B, α : constants
ε 0=K1+K2 (s/ET) (2)
A=K3+K4 (σ/ET) (3)
log ( B exp(Q1/RT) ) = K5+K6 (σ/ET) . (4)
log (exp(Q2/RT) ) = K7+K8 (σ/ET) (5)
K1, K2 , K3, K4 , K5, K6 , K7, K8 : Coefficients of
Equations
Q1, Q2 : activation energy, ET : Young’s Modulus
We calculated the above parameters for the result of
creep tests for used HP-Nb&Ti catalyst tube sampled
from the maximum tube skin temperature portion in
Plant C after 12 years life. Based on these results, the
creep behavior of the catalyst tube was estimated using
the finite element method. Figure 14 and Figure 15
show the results of estimated creep behavior under an
applied stress of 1.3 kg/mm2 (13 MPa), at 900 and 940
degrees C respectively. It is apparent that several per-
centage creep strains will be measured before the tube
life is consumed.
The case of used HP-Nb&Ti catalyst tubes is
shown in Figure 2. “E” in Figure 2 means that destruc-
2004
tive examination, including creep test was done for the
tube sampled from the actual furnace in order to esti-
mate the remaining life. “N” in Figure 2 means that
non-destructive testing was performed for all or half of
the tubes in the actual furnace to assess remaining tube
life. The non-destructive test method used was the
‘H’-Scan inspection procedure, which was developed
by IESCO (International Energy Service Company).
Figure 16 shows the schematic diagram of the ‘H’-Scan
instrument attached to a catalyst tube. The instrument
has four sensors, which are (1) eddy current, (2) ultra-
sonic attenuation, (3) tube wall thickness measurement
by ultrasonic, and (4) tube outer diameter by electric
caliper4).
Conclusion
We summarize below the results of examination of
used HP-Nb&Ti catalyst tubes after more than 10 years
of use in actual steam reformer furnaces.
Metallurgical stability of HP-Nb&Ti material after
use at elevated temperature service is better than that of
HK40 and IN519 materials.
1. Creep rupture strength of HP-Nb&Ti mate-
rial is higher than that of HK40 and IN519
materials, especially, after use at elevated
temperature.
2. Measuring the change of inner diameter is
a useful method to estimate the remaining
tube life, as the same situation as with
IN519 materials.
3. The relationship between the deformation
and the life of catalyst tube material is pro-
vided by the constitutive creep equation for
used HP-Nb&Ti material. It is noted that
the creep strain under applied stress and
service temperature will reach several per-
centage points before the tube life is used
up.
References
1. T. Mohri, K. Takemura and T. Shibasaki,
“Application of Advanced Material for
Catalyst Tubes for Steam Reformer”, Am-
monia Plant Safety & Related Facilities,
33(1993) 86
2. T. Shibasaki, T. Mohri and I. Kojima,
“Management Guide for Remaining Life of
43 AMMONIA TECHNICAL MANUAL
 Catalyst Tubes”, Ammonia Plant Safety &
Related Facilities, 43(2002) 224
3. T. Shibasaki, T. Mohri and K. Takemura,
“Remaining Life Assessment of Nb-
Containing Catalyst Tubes”, Ammonia
Plant Safety & Related Facilities, 35(1995)
163
4. B. E. Shannon and N. Smith, “Assessing
Creep Damage Using NDE Techniques”,
Ammonia Plant Safety & Related Facili-
ties, 38(1998) 104
HK40 IN519 HP-Nb,Ti
4000
Cumulative Number of Catalyst Tube

Out of Furnace

3000

2000

1000

0
1968 1975 1982 1989 1996 2003
Year

Figure 1 Change of Catalyst Tube Materials in

Steam Reformer Furnaces,Which Were Installed
Upper Part of Catalyst Tube
by Chiyoda Corporation

Lower Part of Catalyst Tube (Max.

Tube Skin Temperature)
25µ
Photograph 1 Microstructures of HP-Nb&Ti
Catalyst Tube After 12 Years Use
Figure 2 State of Examinations for Sampled Cata-
lyst Tubes

AMMONIA TECHNICAL MANUAL 44 2004

 250
Burner Side
Out of
Furnace Tube Side

Vickers Hardness (Hv)

200

150
0 20 40 60 80 100
Out of Furnace Location (0%:Top of Catalyst Tube ---- 100%:Bottom of Catalyst Tube)

Figure 3 Hv Distribution of Used HP-Nb&Ti

Catalyst Tube in Plant A

240

220

Vickers Hardness (Hv)

200

180

160
Upper Part of Catalyst Tube Out of
Furnace

140
0 20 40 60 80 100
Location (0%:Top of Catalyst Tube ---- 100%:Bottom of Catalyst Tube)

Figure 4 Hv Distribution of Used IN519 Catalyst

Tube in Plant U
0.2% Proof Stress Tensile Strength
60
0.2% Proof Stress, Tensile Strength (kg/mm )

50
2

40

30

Lower Part of Catalyst Tube (Max. 20

Tube Skin Temperature)

25µ 10

0
0 2 4 6 8 10 12 14
Used Period (Year)

Photograph 2 Microstructures of IN519 Catalyst Figure 5 Change of Tensile Strength of HP-

Tube After 12 Years Use Nb&Ti After Using in Plant A

2004 45 AMMONIA TECHNICAL MANUAL

 10
Elongation Reduction of Area
9 Test Data (13 years of using)
8 Master Curve of Creep Rupture Strength
14 7
6
12
5
Elongation & Reduction of Area (%)

Stress (kg/mm )
2
10 4

8 3

6
2

1
0 21 22 23 24 25 26 27
0 2 4 6 8 10 12 14
LMP (C=17.5977)
Used Period (Year)

Figure 6 Change of Tensile Ductility of HP- Figure 9 Creep Rupture Strength Master Curve
Nb&Ti After Using in Plant A of HP-Nb&Ti After Use in Plant A
6
10
40

12 years used
As Cast Condition

30

Rupture Time (hour)

Elongation (%)

5
20 10

2
10 1.3 kg/mm
2
1.5 kg/mm
2
1.7 kg/mm
2
1.9 kg/mm
2
0 2.1 kg/mm
0 200 400 600 800 1000
4
10
Temperature ( C) 860 880 900 920 940
Temperature ( C)
Figure 7 Change of Tensile Ductility of HP-
Nb&Ti After Use in Plant C Figure 10 Temperature vs. Rupture Time of HP-
10 Nb&Ti After Use in Plant C
9 Test Data (12 years of using) 10
6

8 Master Curve of Creep Rupture Strength 2

2.1 kg/mm
7 2
1.9 kg/mm
6 2
1.7 kg/mm
2
5 1.5 kg/mm
2
1.3 kg/mm
Stress (kg/mm )

4
2

Rupture Time (hour)

3
5
10

1
21 22 23 24 25 26 27
4
10
LMP(C=17.9695) 860 880 900 920 940
Temperature ( C)
Figure 8 Creep Rupture Strength Master Curve Figure 11 Temperature vs. Rupture Time of HP-
of HP-Nb&Ti After Usie in Plant C Nb&Ti After Use in Plant A

AMMONIA TECHNICAL MANUAL 46 2004

 6
10

aa
Estimated Rupture Time (hour)

Creep
aa
Strain
aa
(%)
aa
aa
10
5 30,000 hrs
aa

2
IN519 (1.5 kg/mm )

HP-Nb&Ti (1.5 kg/mm2)

IN519
2
(1.7 kg/mm ) Figure 15 Estimated Creep Curve at 940 C Based
2
HP-Nb&Ti (1.7 kg/mm ) on The Result of Modified Theta Projection Con-
2
IN519 (1.9 kg/mm )
2
cept for Used HP-Nb&Ti Material in Plant C for
HP-Nb&Ti (1.9 kg/mm )

10
4 12 Years
860 880 900 920 940

Temperature (degree C)
1: Eddy Catalyst Tube
Figure 12 Comparison of Creep Rupture Strength Current
Between IN519 and HP-Nb&Ti Materials After T t Bolt to Fix
2: Outer Diameter
Use of 12 Years Measurement by
the
Instrument
Caliper On Tube
1 Air Motor to
3: Tube Wall Move
Thickness th I t t
0.8
Measurement by UT

4:UT Attenuation
Change of 0.6
Inner Diameter
Brush to Clean
(%)
the
0.4
Tube Outer

Outline of ’H’‐Scan Instrument (IESCO)

0.2
Figure 16 Schematic Diagram of ‘H’-Scan In-
0 strument Developed by IESCO
0 20 40 60 80 100

Figure 13 Distribution of ID Along the HP-Nb&Ti

Cat. Tube After Use in Plant C

Creep
Strain
(%)
30,000
hrs

Time (hour)

Figure 14 Estimated Creep Curve at 900 C Based

on The Result of Modified Theta Projection Con-
cept for Used HP-Nb&Ti Material in Plant C for
12 Years

2004 47 AMMONIA TECHNICAL MANUAL