Niobium I

n the past, refining was done in ves-

sels made of Type 300 series stainless
steels (SS). Higher pressure and tem-
perature were addressed by use of

Stabilized
nickel and Ni-Cr-Fe solid solution alloys.
The processing of petroleum promised
innumerable possibilities. Increased ca-
pabilities and efficient processes were
designed and called “thermal cracking”

Alloys in Steam
or “catalytic reforming.”

Catalytic Reforming
Catalytic reforming is designed to

Hydrocarbon
upgrade the quality of petroleum byprod-
ucts. This process takes place in tubes that
are suspended in a furnace, where a
variety of reactions occur in the presence
of some catalytic agent. The tubes are fed

Reforming
with a hydrocarbon and steam mixture.
The catalyst synthesizes ammonia (NH3)
by chemically combining hydrogen and
nitrogen under pressure. The catalytic
reaction of the steam and hydrocarbons
Ramesh Singh, Gulf Interstate Engineering, Houston, Texas mixture at an elevated temperature sup-
plies hydrogen for the reaction.
Cn H m + nH2 O  nCO + ( m/2 + n )H2   (1)
 
(reforming reaction)
This article explains the steam reforming process
CO + H2 O  CO2 + H2  
  (2)
and discusses the development of niobium-stabilized Since the number of moles of the
product exceeds the number of moles of
microalloys. Also presented are the advantages of reactants, this is an endothermic reaction
and requires energy input from burning
these alloys over materials commonly used natural gas or naphtha. The high tem-
perature causes axial stress in the body of
for steam reformer tubes. the tube, leading to longitudinal creep.
The pressure in the tube creates hoop
stress that develops circumferential creep.
Both kinds of stress reduce the life of the
reformer tube.
These actions create a need for special
material that has the best possible creep
strength and still meets the service condi-
tions in the furnace. Applicable tube mate-
rial must have the following properties:
•  High temperature resistance under
internal pressure

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 M AT E R I A L S S E L E C T I O N & D E S I G N

FIGURE 1

•  High creep resistance

•  Resistance to attack from furnace
contaminates
These properties aim to achieve high
creep rupture strength.

Important Aspects to
Consider in a Reformer
System
The following six aspects are consid-
ered in the design of an efficient reformer
system.

Reformer Tubes—
Material of Construction Schematic diagram of a reforming plant.
Reformers are centrifugally cast Fe-
Cr-Ni tubes. A typical tube is machined
and has a wall thickness of 12 to 19 mm
FIGURE 2
and an internal diameter of 88.90 to
100.98 mm. The wall thickness is kept as
low as possible to reduce the weight and
the risk of developing longitudinal creep
stresses. Figure 1 illustrates the schematic
arrangement of a reforming plant. Figure
2 shows the tubes in an actual furnace.
Reformer material affects throughput
and the energy consumption. Conven-
tionally, alloys HK 40† (UNS J94204), HP
35†, HP 45†, IN 519† (UNS N08367), or
equivalent alloys have been used.

Physics of Grain Structure

Irrespective of the composition of the
material, the cast structure of these alloys
varies according to the cooling rates.
Within a controlled range, these alloy
castings may have the following common
grain structures (Figure 3):
•  Columnar gain adjacent to skin of
the cast tubes
•  Equiaxed structure
The austenitic cast materials tend to
have more columnar structure than ferrite
structure, often ranging from 90 to 100%
columnar structure when cooling is con-
trolled. This property of austenite is the
†
Trade name.
Rows of reformer tubes in a furnace.
key factor in the choice of conventional or
niobium-stabilized alloy variants.
Niobium-stabilized alloys have austen-
itic structure; hence, on solidification,
they develop large columnar grains. The
foundry practice to cool the outer surface
of the mold to arrest austenite structure
forms the nuclei and helps in the forma-
tion of the columnar grain by increasing
the cooling rate in the direction of heat
travel. At solidification, the isotherm
moves nearly equal to the growth rate of
the macrostructure. The columnar
growth is obtained in dendrite as well as
austenitic alloys. The dendrite or eutectic
fronts grow at the speed Vs. This speed
is directly related to that of the isotherm
(Vm). This is but only one factor in the
promotion of columnar structure. The
other variables are temperature-related.
December 2009  MATERIALS PERFORMANCE  3

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 M AT E R I A L S S E L E C T I O N & D E S I G N
FIGURE 3
(a)
Grain structure of reformer tubes. (a) Fine columnar grains at the tube skin with
large well-oriented grains in the rest of the pipe wall. (b) Complete equiaxed
structure in ferritic steel.
•  Δ Tc = Temperature at which co-
lumnar grains starts to form
•  Δ Tn = Temperature at which nu-
clei are formed
•  Δ Te = Temperature at which
equiaxed solidification starts
Under ideal conditions, the 100%
columnar growth can be predicted using
Equation (3):
G > A ⋅ No1/3 {1 – ( ∆Tn / ∆Tc )3 }∆Tc   (3)
 
where No = density of grain at Tn and
A = constant.
A higher percentage of columnar
structure is one of the important reasons
for selecting a centrifugal cast material
over wrought material for steam hydro-
carbon reformer tubes. The other factors
that would impact the formation of co-
lumnar structure are the superheat tem-
perature, mold rotation speed, and den-
sity of the fluid material.
The Carbon/Niobium Ratio
Carbon as an austenite former and
niobium as ferrite former influence the
creep rupture properties of austenitic al-
loys. Their influence on creep properties
is both positive and negative, depending
on the specific combination of the two
elements in the alloy. Several combina-
tions of these two elements have been
tried. The results were compared to de-
termine how they affect the creep rupture
properties of an austenitic alloy.
4  MATERIALS PERFORMANCE  December 2009
Singh.indd 4
Niobium Stabilized Alloys in Steam Hydrovarbon Reforming
(b)
At a given level of carbon, increasing
the niobium content increases the maxi-
mum creep rupture life. This increase in
creep rupture strength is limited, how-
ever, by the stoichiometric composition
ratio of carbon and niobium—highest
creep strength is obtained at this ratio.
The creep strength of these alloys is basi-
cally the result of the precipitation of
Nb4C3 from solution. The undissolved
niobium carbide (NbC) tends to control
the rupture strength.
Observation of the microstructure
suggests that the dislocations of undis-
solved NbC cause low creep ductility.
Such dislocations nucleate a dense pre-
cipitation around the particles, which
cause added strengthening. But a very
large amount of undissolved NbC causes
reduction in the rupture life. This is as-
cribed to the formation of eutectic during
solidification, causing the undissolved
particles to enlarge, thus increasing the
numbers of dislocation centers and
reducing the localized precipitation
strengthening. Statical analysis has de-
termined that at any given solution treat- stoichiometric composition with carbon
ment temperature, the solubility product
is given as:
[ Nb ][ C] = ks   (4)
 
The amount of niobium present in the
undissolved NbC, NbNbC, is equated to
7.75CNbC. The Nb or C at a solution treat-
ment temperature can be expressed as †Trade name.
FIGURE 4
Equiaxed structure of varying grain sizes
caused by machine vibration during
casting.
total NbT or CT. A quadratic equation can
be derived using the solubility product:
7 . 75(CNbC ) – {7 . 7 5 CT + NbT }CNbC +
NbT CT – ks = 0
    (5)
The equation will give the amount of
carbon in undissolved NbC. Using a
solubility relationship, the amount of
undissolved niobium can be determined.
It is suggested that at 700 °C, NbC avail-
able for precipitation and NbCu (undis-
solved) were significant at 0.1% and the
following relations were derived:  
1. Log e rupture life( ± 18 . 98) = (6)
2 . 44(±2 . 20) + 7 . 6 6NbCppt (±0 . 47 + 1 . 24 NbCu )
2. %elongation ( ± 18 . 98) =
30 . 06 – 48 . 34 NbCppt (±2 4 . 22) (7)
3. %reduction in area 73.16 ( ± 30 . 66) =
73 . 16 – 9 9 . 03NbCppt (±24 . 22) (8)
NbCppt = NbC available for precipita-
tion during testing.
These findings led to several experi-
ments to develop alloys with niobium in
(Nb4C3 composition). UNS N08367 is
one such alloy. The trend to use micro­
alloys has proven most useful to the in-
dustry. Other similar alloys have been
developed to achieve higher creep resis-
tance. The typical composition of modi-
fied stabilized alloys HP Nb † (UNS
10/26/09 8:36 AM

N08367) and the previously mentioned
UNS N08367 are given in Table 1 and
are identified as UNS N08367(CH) and
UNS N08367(I), respectively.
These materials have highly stable
carbide, increased creep strength, higher
durability, and oxidation resistance com-
pared to the conventional materials. The
advantages of using these microalloys are:
•  Possibility of operation at higher
temperature and pressure
•  Reduced reformer wall thickness
•  Increased quantity of catalyst pack-
ing in the same space—this aspect
has been utilized advantageously for
increasing the capacity and reduc-
ing the energy consumption of exist-
ing reformers
Reforming Catalyst
The selection of the correct catalyst is
essential for efficient operation. The fol-
lowing factors affect the performance of
a catalyst.
•  Chemical composition of the cata-
lyst—typically, metallic nickel dis-
persed over some support material
is used. Commonly used support
materials are α-alumina, calcium
aluminates, and magnesia α-alumina
spinel—a crystal system with oxide
anions arranged in a cubic close-
packed lattice and cations occupying
some or all octahedral and tetra­
hedral sites in the lattice.
•  Calcium aluminates are generally
used for naphtha reforming. Mag-
nesium aluminate, as support mate-
rial, has the advantage of higher
surface area. High-temperature
calcined, magnesium oxide (MgO)-
free material is required to prevent
hydrolyzing at temperatures below
572 °F (300 °C).
•  Geometry of the catalyst—the main
mechanism of heat transfer from the
inner tube wall to the gas is through
convection. Hence, the efficiency
Singh.indd 5
M AT E R I A L S S E L E C T I O N & D E S I G N
table 1
Compositions of modified stabilized alloys
UNS N08367(H) UNS N08367(I)
Elements % Composition % Composition
Carbon 0.45 0.25-0.35
Chromium 25 24
Nickel 35 24
Niobium 1.25-1.5 1.5
Titanium 0.1-0.3 Nil
Silicon 1.00 1.00
Manganese (max.) 1.00 1.00
Iron Balance Balance
depends on the gas distribution over •  Dropping pressure in the front end
the catalyst bed. The catalyst with a of an NH3 plant
better geometrical shape results in •  Reducing mass flow inside the re-
lower temperature of the tube skin. former tube, leading to reduction of
firing for the endothermic reaction
Operating Conditions In an NH3 plant, these advantages
Conventionally, the reformers were create an overall reduction in energy
operated at pressures of ~3 MPa, because consumption by ~0.2 Gcal/MT of NH .
the reformer tube material could not
3
withstand higher pressures. The use of Furnace Design
microalloy reformer tubes allows for rela- The furnaces are either top or side
tively higher operating pressure of up to fired. In the top-fired furnace, the process
4 MPa. The reformer reaction yields an and flow gases have co-current flow.
increase in volume of the gases; this allows These furnaces have high heat flux and
a significant saving in compression en- are generally preferred for high capaci-
ergy. Another advantage of increasing the ties. The burners are limited, however,
reformer pressure is that it allows higher and positioned at one level, thus limiting
heat of condensation of the recovered heat adjustment.
surplus steam. The elevation of reformer The side-fired furnace has multiple
pressure, however, tends to shift the equi- burners located at different levels. This
librium toward the left, requiring addi- allows for flexibility to use different burn-
tional firing to bring back process equi- ers to achieve uniform heating, which
librium. provides uniform tube skin temperature
and better heat control. The limitation of
Steam-to-Carbon Ratio this design is capacity, which is overcome
The steam-to-carbon (S/C) ratio is an by providing multiple chambers.
important parameter. The maintenance The efficiency in dispersion of heat is
of this ratio is key to preventing excessive also improved by replacing most con-
deposition of carbon on the catalyst, shift- ventional firebricks and lining the fur-
ing conversion of carbon monoxide (CO), nace walls with ceramic fiber refectories.
and reducing carburization damage to the This helps keep the outside temperature
tube material. Early designs were based <572 °F.
on a S/C ratio of 4.0 to 4.5. With the
development of superior catalysts, which Installation of Pre-reformer
are active at a lower S/C ratio, it is pos- Installing a pre-reformer upstream of
sible to maintain a ratio of 2.7 to 3.0. The the primary reformer is a common design
lower ratio has the advantages of: practice, particularly in the naphtha-
December 2009  MATERIALS PERFORMANCE  5
10/26/09 8:36 AM
 M AT E R I A L S S E L E C T I O N & D E S I G N Niobium Stabilized Alloys in Steam Hydrovarbon Reforming

based NH 3 plants. The pre-reformer
process breaks down naphtha into
methane (NH4), CO, and hydrogen at
~932 °F (500 °C). This allows for the
primary reformer to function purely as a
gas reformer. Other advantages of pre-
reformer are:
•  It allows flexibility in feedstock, in-
cluding liquefied petroleum gas,
naphtha with a higher boiling point,
and kerosene.
•  The primary reformer can act as a
pure natural gas reformer.
•  It acts as a sulfur guard to the cata-
lyst in the primary reformer.
•  It extends the life of the primary
reformer catalyst.
Pre-reformers also reduce the S/C in
the primary reformers. They have been
designed and installed in many fertilizer
plants. This change has generated sub-
stantial energy saving of up to 0.4 Gcal/
MT of NH3.
Conclusions
This work led to understanding the
advantages of niobium-stabilized micro-
alloys over conventional materials for
steam reformer tubes. These alloys have
highly stabilized carbide and high
strength, durability, and oxidation resis-
tance. Tubes manufactured from these
alloys offer the possibility of operation at
high temperatures and pressures, reduced
wall thickness, and increased quantity of
catalyst in the same space.
References
1 R. Singh, “Metallurgy and Weldability
of Steam Hydrocarbons Reforming
Equipment,” thesis paper TWI-2000.
2 S.R. Keown, F.B Pickering, “Effect of
Niobium Carbide on the Creep Rupture
Properties of Austenitic Steels,” ASM
Handbook, Service Conditions and Require-
ments in the Chemical Industry (Materials
Park, OH: ASM), pp. 138-143.
3 B.M. Patchett, R.W. Skwarok, “Welding
and Metallurgy of 20Cr-32Ni-Nb and
HP 45 Castings,” Proc. of Conference
by the Metallurgical Society of CIM,
1998.
4 A. Chitty, D. Duval, “Creep Rupture
Properties of Tubes for High Tempera-
ture Steam Power Plants,” Proc. of Joint
International Conference on Creep, The
Institute of Mechanical Engineers, Lon-
don, 1963.
RAMESH SINGH is a Senior Principal Engineer at Gulf
Interstate Engineering, 16010 Barkers Point Ln.,
Houston, TX 77079, e-mail: rsingh@gie.com. He
specializes in materials, welding, and corrosion. He
has an M.S. degree in engineering management
from California Coast University and gained his
basic metallurgical education from the Air Force
Technical Institute, India. He is a registered
engineer by the British Engineering Council and a
member of The Welding Institute. An eight-year
member of NACE International, Singh has served as
secretary and vice chair of the NACE Houston
Section. He is the author of several journal articles
and paper presentations.

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