Strain-Age Cracking of Alloy 601 Tubes at 600 C: Henrik Stahl

Strain-Age Cracking of Alloy 601
Tubes at 600 C
Metal dusting can cause a significant amount of expensive damage to ammonia, hydrogen, carbon
monoxide and methanol plants. One of the means to limit this development has been to design the
equipment parts, considered subject to metal dusting attack with Alloy 601. This will typically mean
parts subjected to a reformed gas at 600°C (1,HO°F). The risk of stress relaxation cracking of Alloy
601 at exactly this temperature has not previously been reported, but it must be considered a major
risk that has to be dealt with in the design phase.
Henrik Stahl
Haldor Topsoe A/S, Haldor Topsoe A/S, Lyngby, Denmark
Gaylord Smith
Inco Alloys International, Huntington, WV
Sophie Wastiaux
Air Liquide, Champigny-sur-Mame Cedex, France
Introduction for the reforming reaction. This is one of the features
of a Haldor Tops0e Convection Reformer (HTCR).
The carbon activity of the reformed gas necessitates
S
team reforming of natural gas is considered the
most economic process for industrial hydrogen that special care is taken in the selection of materials
production. By this process, a mixture of for the flow channels for the reformed gas. There is a
methane and steam forms hydrogen, carbon monoxide, risk of metal dusting corrosion. As a consequence,
and carbon dioxide while flowing through a catalyst Alloy 601 was selected for certain components of the
bed. Steam reforming is a strongly endothermic HTCR.
process. Heat is therefore required for the reaction, as After one year of operation, one HTCR exhibited
well as for elevation of the reaction temperature. certain kind of cracks in the Alloy 601 components.
Steam reforming can take place in a tubular The cracks were caused by strain-age cracking, which
reformer. A mixture of methane and steam at 500°C has not been observed previously in connection with
(930°F) and 30 bar (435 psi) is flowing through a Alloy 601.
number of catalyst-filled tubes in parallel. The tubes After relevant heat treatment and certain geometrical
are heated on the outside, and the product gas leaves changes of the 601 components, the HTCR has been
the catalyst tube up to 900°C (1,650°F). brought back to normal operation.
The consumption figures of this process are among
other things depending on the feed gas steam to car- Haldor Tops0e Convection Reformer
bon ratio and on the recuperation of the sensible heat
of the reformed gas. The best utilization of this heat is The HTCR is a tubular reformer with bayonet tubes.
by conducting it back to the process as a heat source A number of reformer tubes are placed in a tube
AMMONIA TECHNICAL MANUAL 21 2000

Outlet Reformed
Gas Nozzle.' Gas Outlet
flue Gas
Outlet Feed Gas
Chamber Inlet
Crack "I Flue Gas
Location Outlet
Inlet
Cas Nozzle
Flue Gas
"nib c
Figure 1. HTCR. Figure 2. HTCR tube.
sheet at the top of a vertical shell. A concentric flue Cracks

gas tube surrounds each reformer tube. The HTCR is
shown in Figure 1. Two skid-mounted hydrogen production units, each
At the bottom, the shell is connected to a horizontal with a capacity of 5,000 Nm3/h have been installed in
combustion chamber where hydrocarbon is combusted Belgium. A picture of this plant is shown in Photo 1.
with air to form a flue gas of 1,250°C (2,280°F). This After having been in operation for one year, a crack
flue gas is flowing into the reformer shell and is then was observed at one hairpin close to the outlet header.
conducted through the annular channel between the The location is indicated on Figure 1.
flue-gas tube and the reformer tube to the flue-gas out- The crack was located in the heat-affected zone of
let chamber. It leaves the reformer through the flue- the welding. It had developed in parallel to the weld-
gas outlet nozzle. ing (along the fusion line) and looked like a brittle
The feed gas flows through the inlet gas nozzle at rupture. The micrograph in Figure 3 shows the typical
the top of the reformer shell and is then distributed intergranular crack.
through a manifold system to the inlet hole at the top The material of the outlet manifold system is Alloy
of each reformer tube. The HTCR tube is shown in 601. This alloy was selected because the reformed gas
Figure 2. It now flows down through the catalyst to has a high carbon potential. When the reformed gas is
the bottom end of the reformer tube. It returns through cooled from 900°C (1,650°F) to 600°C (1,110°F) in
the bayonet tube to the top end where the reformed gas the bayonet tube and is flowing further through the
exits via a 90° bend through the reformer tube wall, outlet manifold system, there is a severe risk of metal
the outlet manifold system, and further on to the gas dusting corrosion. Alloy 601 was considered one of
outlet nozzle. the most resistant materials with regard to metal dust-
ing.
The crack resulted from a kind of the so-called
strain-age or stress relaxation cracking. This has not

Figure 3. Skid-mounted Hydrogen Production Units, Belgium.
previously been reported by application of Alloy 601. carbon precipitation that over time (in this case one
However, the subsequent investigations, performed by year) reduces the ductility of the material in hot condi-
TNO, showed that Alloy 601 at a temperature between tion. A condition that may lead to stress relaxation
600°C (1,110°F) and 650°C (1,200°F) will develop cracking.
Stress Relaxation Cracking Phenomenon
Stress relaxation cracking occurs when a material,

because of limited creep ductility, cannot withstand
the inelastic strain imposed upon the alloy. The phe-
nomenon is most frequently confined to the tempera-
ture range of 500-900°C (930-1,650°F), depending on
the alloy. Experience has shown that susceptible mate-
rials usually fail within one or two years of service and
are most often, but not exclusively, associated with
welded joints.
Welded structures are particularly susceptible
because of the potential for high residual stresses (up
to the yield strength of the base material) resulting
from the welding operation that has not been post
weld heat-treated. Test material taken from compo-
nents that have failed by stress relaxation cracking will
still pass all its material specification requirements
Figure 4. Typical Intergranular Crack. adding to the perplexity associated with stress relax-

ation Cracking. (c) A new piece of tube was welded to the outlet
Appearance of the stress relaxation cracking failure manifold.
can aid in confirming this type of failure. The crack is (d) The outlet manifold was taken away and heat-
always located on the grain boundary with cavitation treated in a furnace. The heat treatment consisted in
preceding the crack. Often, in iron-base alloys, the heating to 950°C (1,740°F) and holding this tempera-
crack contains a metallic filament enclosed by a ture for 1 h.
chromium-rich layer. The crack zone is usually hard (e) A connection of the outlet manifold was made to
(Vickers Hardness > 200 Hv). The hardness increase is the new reformer tube outlet pieces.
attributed to intermediate temperature-aging reactions Strain-age cracking or stress relaxation cracking is
often accelerated by prior cold work. known by welded constructions of certain materials at
temperatures between 600-650°C (1,110-1,200°F),
Available Materials and Post Fabrication such as Alloy 800, Alloy 617, Alloy 602 CA and oth-
Heat Treatments ers. However, 601 has not been considered susceptible
prior to this.
Alloys containing the age hardening elements (Al,
Ti, Nb plus C) are susceptible to stress relation crack- Conclusion
ing when placed in service with the age hardening
temperature range. The propensity to develop stress Metal dusting can cause a significant amount of
relaxation cracking increases with grain size and expensive damage to ammonia, hydrogen, carbon
retained cold work. Thus, an alloy, such as mill monoxide and methanol plants. One of the means to
annealed (ATSM grain size < 5) INCONEL Alloy 690 limit this development has been to design the equip-
(0.03% C max.) would be a highly resistant alloy to ment parts, considered subject to metal dusting attack
stress relaxation cracking. Many typical alloys for use with Alloy 601. This will typically mean parts subject-
within refineries, and chemical and petrochemical ed to a reformed gas at 600°C (1,110°F). The risk of
facilities contain levels of C (0.05-0.2%), Al (0.1- stress relaxation cracking of Alloy 601 at exactly this
0.5%) and Ti (0.1-1.5%) which can lead to stress temperature has not previously been reported, but it
relaxation cracking unless the alloy is given a post must be considered a major risk that has to be dealt
fabrication heat treatment. The temperature, optimized with in the design phase.
for each alloy, eliminates the effects of retained cold The means to avoid or minimize the risk of cracks
work and welding stresses, coarsens the grain bound- could be one or more of the following:
ary precipitates, minimizes any Cr gradient adjacent to • Arrange the process design so as to avoid tempera-
the grain boundary, which may have resulted from Cr- tures between 575°C (1,065°F) and 650°C (1,200°F).
containing carbide precipitation and, finally, establish- • Select a material that combines good resistance
es a grain matrix more likely to form a coarser (less against metal dusting and which does not develop the
damaging) age hardening precipitate. For Alloy 601, precipitation that causes stress relaxation cracking. It
such a temperature is believed to be 900-1,000°C could be Inconel 690.
(1,650-1,830°F) for between one and three hours. • Include proper heat treatment of the reactor and
downstream equipment, which operates in this temper-
HTCR Repair and Modifications ature range.
After having realized the phenomena, it was decided Literature Cited

to take the following actions:
(a) All connections between reformer tubes and out- Van Wortel, J.C., " "Relaxation Cracking in the
let header system were cut. Process Industry an Underestimated Problem," TNO
(b) Tube pieces next to the problematic area were Institute of Industrial Technology, Apeldorn, The
removed. Netherlands.

Strain-Age Cracking of Alloy 601 Tubes at 600 C: Henrik Stahl

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Strain-Age Cracking of Alloy 601

AMMONIA TECHNICAL MANUAL 21 2000

Figure 1. HTCR. Figure 2. HTCR tube.

sheet at the top of a vertical shell. A concentric flue Cracks

AMMONIA TECHNICAL MANUAL 22 2000

Stress Relaxation Cracking Phenomenon

Stress relaxation cracking occurs when a material,

AMMONIA TECHNICAL MANUAL 23 2000

After having realized the phenomena, it was decided Literature Cited

AMMONIA TECHNICAL MANUAL 24 2000

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