Niobium I

Stabilized
Alloys in Steam
Hydrocarbon
Reforming

n the past, refining was done in vessels made of Type 300 series stainless
steels (SS). Higher pressure and temperature were addressed by use of
nickel and Ni-Cr-Fe solid solution alloys.
The processing of petroleum promised
innumerable possibilities. Increased capabilities and efficient processes were
designed and called thermal cracking
or catalytic reforming.

Catalytic Reforming

Catalytic reforming is designed to

upgrade the quality of petroleum byproducts. 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
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 supplies hydrogen for the reaction.

This article explains the steam reforming process

and discusses the development of niobium-stabilized
microalloys. Also presented are the advantages of
these alloys over materials commonly used
for steam reformer tubes.

Cn H m + nH2 O  nCO + ( m/2 + n )H2

(reforming reaction)

CO + H2 O  CO2 + H2

(1)

(2)

Since the number of moles of the

product exceeds the number of moles of
reactants, this is an endothermic reaction
and requires energy input from burning
natural gas or naphtha. The high temperature causes axial stress in the body of
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 conditions in the furnace. Applicable tube material must have the following properties:
High temperature resistance under
internal pressure

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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 considered in the design of an efficient reformer
system.

Reformer Tubes
Material of Construction
Reformers are centrifugally cast FeCr-Ni tubes. A typical tube is machined
and has a wall thickness of 12 to 19 mm
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. Conventionally, 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 controlled. This property of austenite is the

Trade name.

Schematic diagram of a reforming plant.

FIGURE 2

Rows of reformer tubes in a furnace.

key factor in the choice of conventional or

niobium-stabilized alloy variants.
Niobium-stabilized alloys have austenitic 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 formation 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.
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Niobium Stabilized Alloys in Steam Hydrovarbon Reforming

FIGURE 3

FIGURE 4

(a)

(b)

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.

Tc = Temperature at which columnar grains starts to form

Tn = Temperature at which nuclei are formed
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 hydrocarbon reformer tubes. The other factors
that would impact the formation of columnar structure are the superheat temperature, mold rotation speed, and density 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 alloys. Their influence on creep properties
is both positive and negative, depending
on the specific combination of the two
elements in the alloy. Several combinations of these two elements have been
tried. The results were compared to determine how they affect the creep rupture
properties of an austenitic alloy.

At a given level of carbon, increasing

the niobium content increases the maximum creep rupture life. This increase in
creep rupture strength is limited, however, by the stoichiometric composition
ratio of carbon and niobiumhighest
creep strength is obtained at this ratio.
The creep strength of these alloys is basically 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 undissolved NbC cause low creep ductility.
Such dislocations nucleate a dense precipitation around the particles, which
cause added strengthening. But a very
large amount of undissolved NbC causes
reduction in the rupture life. This is ascribed 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 determined that at any given solution treatment temperature, the solubility product
is given as:

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 available for precipitation and NbCu (undissolved) were significant at 0.1% and the
following relations were derived:
(6)
1. Log e rupture life( 18 . 98) =
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 precipitation during testing.

These findings led to several experiments to develop alloys with niobium in
stoichiometric composition with carbon
(Nb4C3 composition). UNS N08367 is
one such alloy. The trend to use micro
alloys has proven most useful to the in[ Nb ][ C] = ks
(4)

dustry. Other similar alloys have been

developed to achieve higher creep resisThe amount of niobium present in the
tance. The typical composition of modiundissolved NbC, NbNbC, is equated to
fied stabilized alloys HP Nb (UNS
7.75CNbC. The Nb or C at a solution treatment temperature can be expressed as Trade name.

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table 1
Compositions of modified stabilized alloys

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 compared 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 packing in the same spacethis aspect
has been utilized advantageously for
increasing the capacity and reducing the energy consumption of existing reformers

Reforming Catalyst
The selection of the correct catalyst is
essential for efficient operation. The following factors affect the performance of
a catalyst.
Chemical composition of the catalysttypically, metallic nickel dispersed over some support material
is used. Commonly used support
materials are -alumina, calcium
aluminates, and magnesia -alumina
spinela crystal system with oxide
anions arranged in a cubic closepacked lattice and cations occupying
some or all octahedral and tetra
hedral sites in the lattice.
Calcium aluminates are generally
used for naphtha reforming. Magnesium aluminate, as support material, 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 catalystthe main
mechanism of heat transfer from the
inner tube wall to the gas is through
convection. Hence, the efficiency

Elements

UNS N08367(H)
% Composition

UNS N08367(I)
% 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

the catalyst bed. The catalyst with a
better geometrical shape results in
lower temperature of the tube skin.

Dropping pressure in the front end

of an NH3 plant
Reducing mass flow inside the reformer 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 .
3
the reformer tube material could not
withstand higher pressures. The use of
Furnace Design
microalloy reformer tubes allows for relaThe 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 capaciergy. 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 burntional 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 condeposition of carbon on the catalyst, shift- ventional firebricks and lining the furing 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 posInstalling 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 naphthaDecember 2009 MATERIALS PERFORMANCE 5

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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

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 prereformer are:
It allows flexibility in feedstock, including 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 catalyst 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 substantial energy saving of up to 0.4 Gcal/
MT of NH3.

Conclusions
This work led to understanding the
advantages of niobium-stabilized microalloys over conventional materials for
steam reformer tubes. These alloys have
highly stabilized carbide and high
strength, durability, and oxidation resistance. 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 Requirements 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 Temperature Steam Power Plants, Proc. of Joint
International Conference on Creep, The
Institute of Mechanical Engineers, London, 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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