Challenges of welding of catalyst tubes and outlet assemblies in Hydrogen Reformers

Jahangir Quluoqlu Taghiyev

Email: jahangir.taghiyev@aramcooverseas.com
Aramco Overseas Company B.V.
Scheveningseweg 62-66
2517 KX The Hague
The Netherlands

ABSTRACT
Austenitic Stainless Steels and Nickel Alloys used in the petrochemicals industry are very effective
processing chemicals at high temperatures but there are certain challenges related to the best combination
of alloying elements and welding consumables to be used. Hydrogen Reforming technology has been
benefitting from many solutions existing for these challenges however, with an ever growing need for
higher temperatures in order to increase the efficiency of reforming furnaces or other production units, the
demand for better materials and joining methods is always present. Alloying elements have various effects
on resistance to creep, to oxidation and corrosion in general. Materials selection and manufacturing play
a vital role in guaranteeing successful performance of Catalyst Tubes and Outlet Headers. Choice of
welding technologies, procedures, consumables, qualification of these and practical execution in field are
also as important. In addition to these, handling of equipment made out of Austenitic Stainless Steels and
Nickel Alloys requires close follow up.

INTRODUCTION
In an attempt to review modern day industrial practices related to catalyst tubes and outlet headers used
in Hydrogen reformers, this equipment is to be discussed from theoretical and practical perspectives. This
is by no means a comprehensive study. However specific may the title of this paper sound, the factors that
affect performance of the catalyst tubes and outlet assemblies are dispersed in various disciplines each of
which requires a separate study.
Basic understanding of Hydrogen Reformer and endothermic processes running in it, is required for
grasping the performance of equipment and materials to be discussed, therefore, an overview of Hydrogen
production will be needed. A closer review of recommended materials, their properties and failure
mechanisms is conducted. Issues related to heat resistant steels such as Nickel-Chromium alloys used for
casting catalyst tubes and Austenitic Stainless steels used for manufacturing of outlet headers are the main
subject of this paper. Eventually the paper will go over welding and repair practices proven to work in the
field.
Main intention is to encourage engineers, quality personnel and project management teams involved in
similar projects to study the mentioned issues and derive lessons for their project needs.

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 HYDROGEN REFORMERS
With an ever growing demand to quality of fossil fuels and lubricants, desulphurization requirements of
fossil-fuel products and also alternative energy sources the need for hydrogen in the world is on the rise.
Hydrogen is ever more frequently being used for hydrogenation and hydrocracking for obtaining higher
quality and more pure fuels but also has a wide application in chemical industry and electronics (semi-
conductors). Low Sulphur, olefins and aromatics requirements in fuel for combustion engines is perhaps
the largest driver for hydrogen production industry. This is explained not only by environmental
concerns but also by more efficient, modern internal combustion engines that needs these cleaner fuels.
Since in nature hydrogen is almost nonexistent in its pure form, industrial production of hydrogen is the
only practical way to obtain it. This means extraction of H2 from Hydrogen containing compounds such
as hydrocarbons and water, which has its well-known complications. Specific equipment and processes
have been and are continuously being developed for producing Hydrogen on various scales but also for
application of it as for example an alternative energy source.

Figure 01: Hydrogen plant(1)

There are various technologies for hydrogen production known in the industry (e.g. reforming of natural
gas, gasification of coal and biomass, water-electrolysis and others). They are varying in feed materials,
effectiveness of separation process, various degrees of purity of product, also in capacity and of course
many other factors. Most common process used today is however steam reforming and in particular steam

(1)
Air Liquide, Germany

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reforming of methane (natural gas) despite its tendency to consume large amounts of energy. Methane as
feed can also be supplied in a mix of hydrocarbons such together with ethane, propane. Some feeds may
also include heavier hydrocarbons such as naphtha. The difference of feed is affecting design and
operation of the plant.
One of the effects is for example in case of natural gas or refinery gas, the feed is delivered by pipelines
from a pipe grid, whereas naphtha or LPG usually comes from a nearby storage tank.
At pretreatment part of the plant, which is an optional stage actually, desulphurization and dechlorination
is taking part. These are poisonous contaminants of the feed. At this section feed is pre-heated to
approximately 200C then fed into a treatment unit to remove unwanted contaminants. Here feed is mixed
with steam and further heated to 550-6500C. Now it is ready to enter the steam reformer, this complete
stage however may be skipped in some plants.
The so called firebox is containing the burners and the catalyst tubes. Box itself is laid with several layers
of refractory materials including bricks and refractory cement. Here, inside the tubes, main chemical
reaction is occurring in presence of heat and catalysts. The heat required for reaction is obtained by the
combustion of fuel gas and purge/tail gas from the PSA system. Feed gas, after passing through catalysts
is already converted into a mixture of hydrogen, carbon monoxide and carbon dioxide with some
remaining unconverted feed in form of methane. The catalyst tubes, which due to the high temperatures
involved have to be made from Nickel-Chromium alloys, are discussed in more detail further in this paper.

Figure 02: Typical equipment of a steam reformer

Next stage is the Shift Conversion reaction, where carbon monoxide is shifted with steam to increase
hydrogen yield and decrease the unwanted by-product carbon monoxide. Running in parallel also there is
convection section processes for which the flue gas from the burners is being used.
At the PSA Unit hydrogen is separated using Pressure Swing Adsorption. The hydrogen, because of its
molecular structure, is recovered in series of vessels filled with layers of different absorbers, where
pressure is being raised in cycles close to the feed pressure and dropped to lower pressures to allow

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impurities to be removed. The PSA allows to reach hydrogen purities higher than 99.999 % and impurities
of less than 1 ppm including carbon monoxide and remaining methane. The PSA tail-gas, which contains
the impurities, can then be sent back to the fuel system to be used as fuel gas for burners.
Apart from fire box, catalyst tubes and PSA Unit, following equipment is typical equipment used in
hydrogen reformers:
• Sub-headers – manifolds collecting • Spring supports systems carrying the load
process gas from catalyst tubes and of catalyst tubes and reacting to

•
feeding into transfer line; variations in lengths and other
Outlet header (also called transfer line movements of the tubes during operation.

•
header), manifold taking reformed gas These are placed on top of the firebox;

•
further to shift conversion; Burners installed either on top, side walls

•
Coils for various processes routed or bottom of the firebox;

•
through Pigtails – smaller diameter, bent tubes at

•
Convection Section in order to utilize the inlet and outlet of catalyst tubes

• •
flue gas heat; Transition and other ductwork;

• •
Steam Drum; Flue gas tunnels (troughs);

•
Process Gas Boiler (PGB); Flue gas stack;
Air draft fan;

Steam reformer is an integral part and a critical asset for successful operation of the hydrogen
plant. They are also the most expensive unit in the plant. A reformer only, without auxiliary
equipment and catalysts, costs above 3 MM €. Retubing of a reformer itself may cost more than
1MM €, without accounting the daily loss of profit. Therefore it is vitally important for plant
owners to ensure proper design, materials selection, planning, execution and maintenance of any
petrochemicals plant

CATALYST TUBES AND OUTLET HEADERS

Reforming technology has been constantly going to higher temperatures in order to increase the
efficiency of the processes and therefore constantly new materials had to be developed for these
temperatures. High temperatures combined with constant loads are two known unavoidable factors
the industry has to deal with.
Catalyst tubes, which are usually 125-130mm in diameter and 10 to 13 mm thick, due to high
operation temperatures are prone to thermal degradation, namely creep. Creep is known to be
primary damage mechanism of catalyst tubes. Other reasons leading to catalyst tubes failure can
be tubes overheating due to carbon build up resulting from blockage created by broken catalyst
parts. Broken catalyst parts on their own are often also a source of local overheating in a tube.
Fatigue due to frequent emergency shutdowns of the reformer is also one of tube failure causes.

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 Figure 03: Temperatures in firebox
Tubes nowadays are usually designed to minimum 100,000 hours of operation that is slightly more
than 11 years but practice shows that re-tubing is sometimes needed at much earlier intervals. This
is due to above mentioned issues and the fact that operation temperature variations do dramatically
affect service life. Depending on used materials, a 150C increase in temperature can reduce lifetime
by roughly 30-50%.
Catalyst tubes get their heat by radiation from flue gas, from refractory lined walls and from flame
of the burners. Depending on the burner placement, some of these supply more heat than the others
(e.g. side wall burners increase radiation from refractory lined wall and from flame compared to
the case of top or bottom burners). This is why the firebox is sometimes called the radiant box.
Tube temperatures here depending again on burner displacement, may get from 6500C to about
9600C at various parts of its length.
Material development has come long way from using raw stainless steels to usage of high nickel-
chromium alloys with special inhibitors added to delay creep processes.

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 Figure 04: Catalyst tubes installed in radiant box
The stresses applied at above the recrystallization temperatures are promoting dislocation
movements, vacancy diffusions and grain boundary sliding and diffusion in the microstructure.
These trans-granular and inter-granular processes are related to strain growth.
Creep has been assigned various number of stages in literature. We will use three stages
classification: primary, secondary and tertiary.
In primary stage damages are hardly noticeable but plastic deformation as well as hardening is
taking place. Aging of microstructure is in progress, carbide precipitation (e.g. M23C6) at grain
boundaries is taking place and cementite (Fe3C) is setting in pearlite/ bainite.
The secondary creep stage is when creep voids are growing and merging together. Although the
creep speed (strain rate) is constant in this phase, the microstructure however is starting to loosen
up already. It is at this stage that the creep strength of material shows itself by keeping the
microstructure put despite the started processes of merging dislocations and microscopic cracks
that start to develop then.
The next stage is associated with significant acceleration of creep strain rate (exponential growth).
The microstructure, which has begun to lose its strength already is under more stress and creep
fracture is being formed although initially restricted.

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 Figure 05: Formation of creep fractures1
Creep damage initiates always from the inner side of the tube. In most cases catalyst tubes damaged
by creep are failing in series and not individually.

Figure 06: Creep related damage is typically starting from inner wall of the tubes; HK-40
material2

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 Figure 07: Creep damage of reformer tubes at bottom section3
In case of outlet assemblies the heat is coming from the process gas running in them. Therefore
sub-headers and outlet headers are lined with refractory lining, which also allows less expensive
steels to be used for their fabrication. In addition to creep, which is actually not so severe in this
case (except for pigtails), stress relaxation cracking and metal dusting are of core problems to be
faced with.
Austenitic steels operating at 480-8150C may also get sensitized by chromium carbides
precipitation at grain boundaries, in presence of oxidizing mediums, which may lead to chromium
depletion and result in inter-granular corrosion.

Figure 08: High alloy welds of Bull Tee on a sub-header cracked

Erection practices here are as important as materials selection and welding. Subheaders are known
to get cracks due to inadequate supporting or improper hoisting arrangement during lifting.

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 Figure 09: Relaxation cracking of 347H inlet header working at 500-750C. Brittle, inter-
granular failure.

MATERIALS SELECTION
Austenitic creep resistant steels are suitable up to 7000C, which might be useful for outlet headers
but not for catalyst tubes.
Nickel base alloys are used for higher temperatures. In presence of oxidizing agents, at
temperatures above 6500C the protective oxide layer formed by alloys with Cr contents up to 20%
is destroyed therefore cast alloys with higher Cr content are used. These are known as Nicrofer
(NI-Cr-Fe) alloys.
Initially wrought stainless steels with low carbon contents were being used for catalyst tubes till
roughly 1960’s, then centrifugal casting of creep resistant steels provided materials with higher
carbon content and higher alloys suitable for higher temperatures.
Cast materials have finer grain than wrought steel and materials are therefore stronger. HK40,
followed then by HP Modified and now super alloys using rare earth metals, all are allowing
designers to go to ever higher temperatures in reformer design.
The stable microstructures so important for resisting to creep are achievable by following:
•
•
Solid solution hardening with Cr, Mo, Co, W.

•
Carbides formation by addition of Ti, Nb, V, B, Zr
Precipitation hardening with Al, Ti, Nb, (fine precipitates evenly distributed in

•
microstructure inhibit creep)
Heat treatment (in order to achieve precipitation)
Although Al, Cr, W, Mo, V, Al, and Si are also forming carbides they are however also limiting
austenite loop (temp. range in which austenite structure exists). Chromium is however, required to
increase resistance to oxidation and corrosion. Ni is therefore added to stabilize austenite structure.
However Ni is not sufficient to achieve fine grain carbides. So Nb and Ti are added stabilize the
material at high temperatures. They refine the carbides and create a more even and stable
distribution of them along the grain boundaries. In order to promote formation of strengthening σ

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(sigma) phases in microstructure Mo and W are added. Al and Si besides increase oxidation
resistance and contribute to protective film formation in presence of Cr.
Table 01
Alloys mostly used for Outlet systems and Catalyst tubes; Prices are as for 2009

Alloy name, Standard / Classification per Suitable for Price Additional info
if known Grade EN 10095 T0C € / kg
321H ASTM A 1.4941 8154 14.90 18Cr10Ni+Ti
312
347H ASTM A 1.4961 8154 14.90 18Cr10Ni+Nb+Cb
312
Alloy 800H ASTM B 1.4876 9854 44 21% Cr, 32% Ni,
407 0.1% C, +Ti+Al
HK40 ASTM 1.4848 10104 16 25Cr20Ni; Centrif.
A531 cast tube
HP Mod. 1115 19 25Cr35Ni+Nb;
Centrif. cast tube
HP 25Cr35Ni+Nb+Ti;
Microalloy Centrif. cast tube
1125 24 25Cr45Ni+Nb;
Centrif. cast tube

Table 02
Chemical composition for Alloy 800, 800H, 800HT5

Nowadays Alloys 800 is not used anymore in reformers and outlet systems. 800H and 800HT are
used for inlet / outlet piping and headers.
Alloys with better creep resistance properties help to reduce thickness of tubes without
undermining life span and also decrease the number of tubes. It results in improved efficiency and
longer tube life.

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 MANUFACTURING AND PRE-FAB CONTROL
Catalyst tubes are manufactured by spun casting. Molds of 3 to 5 meters long are used for this
purpose, due to which catalyst tubes are made from several sections, welded together.

Figure 10: Catalyst tube manufacture. Liquid alloy poured into steel mold6
After liquid metals from the furnace are filled into the mold and all checks (ladle analysis and other
controls) and preparations are complete, the mold is spun at around 1500rpm. The tube forms in
the mold due to the centrifugal forces acting on the liquid steel, which solidifies during the process.
The ends of tube section are then cropped, internals are machined and external surface goes
through shot blasting and then to pressure testing.
Outlet headers are normally delivered to erection site with refractory already installed in them and
this may cause some complications in field joints between cone and header and, if the large sized
header is delivered in sections, between individual header sections. Quality of performed welding
is especially important as for example notches and stress concentrators may induce stress
relaxation cracking.

WELDING AND CONSUMABLES RECOMMENDATIONS

Consumables with similar chemical composition to base metals are the best fit for high temperature
applications. Thermal expansion coefficients of consumables must also correspond with that of
base steels.
Table 03 provides recommended types of consumables for corresponding welds from Figures 11.

Figure 11: Weld map of Catalyst tubes SW – Shop Welds; FW- Field Welds

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 Table 03
Consumables recommended for welding of catalyst tubes

Joint Design Base materials Recommended weld Remark

no T [°C] consumable(s)
SW1 640 304H to AWS(2) A5.14 AWS A5.14 ERNiCrMo-3 (625) is
25Cr35NiNbMA ERNiCr-3 NOT recommended due to risk of
embrittlement between 593-760°C.
SW2 930 25Cr35NiNbMA Matching Only matching consumables shall
to be used
25Cr35NiNbMA
SW3 930 25Cr35NiNbMA AWS A5.14 Matching 25Cr35NiNbMA is NOT
to Alloy 800HT ERNiCrMo-3 (625) recommended due to risk of Cr-C at
the Alloy 800HT grain boundaries.

When designing weld joints and preparing Austenitic steels and Nickel Chromium alloys for
welding bevel size is important especially for field welds. For a single V joint it is normal for
opening to be 80-850C
Preferable are processes using shielding gas such as TIG, however for larger thicknesses SMAW
is also being used for filling paths, provided electrode selection is appropriate.
If dissimilar welding is to be performed it is preferable to get manufacturer do buttering in his shop
prior to shipping, so that complications related to dissimilar joints are avoided. In any case,
buttering is recommended even if weld is a field joint.
Preheat to 500C is sufficient. Controlled cooling must be applied in order to allow trapped gasses
to escape. Critical welds shall be welded, if possible in manufacturing shop.

Figure 13: Weld map of Subheader, Bull Tee and Cone

(2)
Here and elsewhere in this paper: American
Welding Society; 8669 NW 36th St, Doral, FL 33166,
USA

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In order to prevent nitrogen pick up during welding filler materials are alloyed with Al, Ti or Nb,
that remove nitrogen by forming nitrides. To avoid hot cracking, to which Nicrofer alloys are prone
due to delayed solidification, controlled heat input and stringer bead welding shall be used. Energy
input shall be limited to 5 to 15 kJ/cm and interpass temperature shall be not more than 1500C
Table 04
Consumables recommended for welding of Subheaders, Bull Tee and Cone
Joint Design Base Recommended
no T [°C] materials weld consumable(s)
SW4*/ 900 20Cr33NiNb Matching
SW5 to
20Cr33NiNb
SW6/ 930 20Cr33NiNb Matching
FW4 to Alloy 20Cr33NiNb
800HT
FW1 640 304H to 304H AWS A5.9 ER308H/
ER19-10H
FW3 900 20Cr33NiNb Matching
to
20Cr33NiNb
FW5 425 20Cr33NiNb AWS A5.14
to A387 Gr.11 ERNiCr-3(e.g. UTP
A068HH or Nicro
82)

Bevel slopes on both sides shall be fused first and then the middle of the puddle. Peening for stress
relieving purposes is preferable for intermediate passes.
As mentioned earlier tubes are designed for 100,000 hrs operation. In order to prove the suitability
of cast tubes for this design life, prior to installation tubes have to be creep tested. For this purpose,
tubes are loaded at operation loads and subjected to specified temperatures (usually several
measurement points 8500C, 9000C and/or 9500C). Creep Rupture test is a must for materials
subject to creep due to service conditions. Tensile strength under creep conditions, load time till
fracture and the yield point under creep are values to be obtained during the test.
ASTM(3) E139 in US and EN ISO(4) 204 in €pe are the standards for creep testing materials and
welded joints. These tests help to determine creep elongation / strength and time to creep rupture.
EN ISO 204, describes the single-axis creep test as a method to determine creep when force is
applied along the axis of the test piece. For this test the specimen, clamps and the transducer should
be brought into thermal equilibrium. Test force shall be applied only after thermal equilibrium has

(3)
Here and elsewhere in this paper: ASTM International; 100 Barr Harbor Dr.; West Conshohocken, PA; 19428-
2959; USA
(4)
Here and elsewhere in this paper: International Organization for Standardization; Chemin de Blandonnet 8; CP
401; 1214 Vernier, Geneva; Switzerland

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been maintained for 1 hour. It must be ensured that the test piece is not bent or rotated during test
and the force is applied smoothly and swiftly. Test equipment produces stress-strain and Time-
Elongation diagrams for calculating remaining (or design) life of the materials. Larson-Miller
diagrams

Figure13: Macrostructure of creep tested catalyst tubes is examined for percentage of

columnar grains vs equiaxed grains
As mentioned earlier, normally catalyst tubes are designed to run without need for replacement for
11 years or more. Every plant trip (unplanned, emergency shutdown) is reducing the service life
of catalyst tubes. For this reason creep tests are sometimes specified to be “interrupted” in order
to simulate shutdowns and their effect on creep properties of materials. Careful monitoring of the
overall plant condition is important for maintenance decision making process.
Practice shows that catalyst tubes shall be replaced if tube diameter has increased for 5% or more,
which in worst cases have been reached as early as 2nd year of tubes service life!

MAINTENANCE AND REPAIR

Operational data alone is not a reliable reference for analyzing remaining life of catalyst tubes but
can be helpful in defining inspection areas. However, as practice shows such data is not always
present.
Tube removal during plant shutdowns for metallurgical analysis combined with NDT of not
removed tubes may provide required, reliable data and reduce the complications related to tube
removal.
Various inspection technologies exist for evaluation of life expectancy of catalyst tubes. Acoustic
Emission testing of tubes has been demonstrated to be more sensitive to creep damage. Less
sensitive UT will not always detect early stage of thermal degradation7

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Visual inspection as well as overall temperature, thickness and general process monitoring systems
can give a good indication of process or mechanical complications to be attended for preventing
reformer failure.
Remaining life of catalyst tubes can be estimated by diameter increase. Rule of a thumb is that if
it increases for more than maximum 5% the tube shall be replaced. In good, operation diameter
shall not increase by more than 3% in diameter at the end of its life time8.
Tube wall temperature measurement is an important practice for identifying existing problems
before they lead to a failure. Infra-red optical pyrometers adjusted for emissivity and background
radiation are used.
But overheating, most of the time when it is late, can also be seen visually and depending on the
pattern the cause can be estimated. As mentioned previously, catalyst breakage can cause carbon
formation and related to that blockage.
Handling of catalysts during transportation, storage, loading is therefore important. Time of
catalyst loading and methods are to be carefully reviewed.
Hydrotesting of the steam system needs to ensure that there is no water carryover into the catalyst
tubes.
For outlet headers it is much simpler to spot a problem, since these are outside. Temperature
indicative paint swiftly demonstrates by “hot spots” the existence of problematic areas, where heat
is reaching the metal wall in more than designed levels.

DELIVERY AND STORAGE

It is important to prepare shipment and storage of catalyst tubes and outlet headers in a manner
that will ease subsequent installation (e.g. tubes assembled in sections with pre-welded tube pups
and support elements; outlet header with installed cone and Bull Tee).
Storage outside is acceptable however contamination by carbon dust and elements shall be
avoided.
Upon receipt it is advisable to perform visual inspection for damages, rusting and PMI.

CONCLUSIONS
Despite the complex nature of equipment and sophisticated alloys used for the applications
successful operation of catalyst tubes and outlet headers is possible if the best practices in the
industry are applied. Nickel alloys stabilized by Nb, Ti have proven themselves as a best fit for
the high temperatures involved, however research shall be continued to find solutions with
higher carbon content alloys that will further strengthen creep resistance. Outlet headers
fabrication and catalyst tubes erection are the processes to be closely monitored by end user to
guarantee quality performance.

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 ACKNOWLEDGMENTS
The author appreciates help of Mr. Yasser Y. Shafie – AOC QMD Head – for his support and
inspiration during this work as well as QAU team of AOC for temporarily relieving the author
from other tasks for this activity.

REFERENCES
1. Markus Holthaus: GSI SLV - Creep fractures (International Welding Engineer course material)
2. J.M. Brear, J.M. Church, D.R. Humphrey and M.S. Zanjani “Life Assessment of Steam
Reformer Radiant Catalyst Tubes – the use of damage front propagation methods” p.9
3. Photo cortesy of Haldia Refinery, Indian Oil Corporation Limited
4. API Standard 530, Fifth edition, p.15 / ISO 13707:2001 (E)
5. Special Metals. Alloy 800/800H/800HT data sheet.
6. Photo courtesy of Manoir
7. John M. Rodgers “Acoustic Emission Testing of seam welded high energy piping systems in
fossil power plants”; p.293
8. Azmi Abdul Wahab, Milo V. Kral “3D analysis of creep voids in hydrogen reformer tubes”;
p.222

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