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Casale Chemicals pure oxygen

autothermal reformers burners

Introducion ly constrained by the size of the SMR.

Therefore, ATR unleashes the full po-
may be high, up to 30-40 bar. Soot-
free operation is achieved through op-
tential of some synthesis reactor de- timized burner design.
Hydrogen and synthesis gas (a mix-
signs (such as the Casale isothermal
ture of hydrogen and CO) are the ma-
Methanol reactor) which can be scaled
jor route from hydrocarbons (e.g. nat-
up to capacities thought unreachable
ural gas) to many important chemicals
in single train design a few years ago.
such as methanol, Fischer-Tropsch liq-
Oxygen blown ATR reactors can also Casale Group has been active in the
uid fuels, alcohols and aldehydes from
be employed in combination with SMR field of syngas production for several
oxo-synthesis and ammonia.
(two-step reforming) where the ATR is years and has acquired extensive ex-
Over the past 50 years the tubular
installed downstream of a steam re- perience of partial oxidation, second-
steam methane reformers (SMR) have
formers operating with high methane ary reforming and autothermal reform-
been the most common technology ap-
slip and/or with the addition of nat- ing applications of various kinds and
plied to syngas production. The main
ural gas to the synthesis gas stream capacities operating at different con-
drawbacks of SMRs are the high com-
between the steam reformer and the ditions.
plexity, huge plot area, high invest-
ATR. This solution can be used either Casale has developed, and success-
ments costs especially for high ca-
for new plants or as a retrofit for old fully commissioned, proprietary design
pacity single train applications and
plants in which the installation of an burners for most reformers’ applica-
finally the difficult scalability to ultra
ATR downstream the SMR offers a very tions including:
– high capacity single train applica-
cost effective solution to significantly - Burners for Secondary reformer of
tions.The alternative technologies are
increase the plant capacity, with low ammonia plants with capacities rang-
Autothermal Reforming (ATR) and par-
investment and risks and a short pay- ing from 700 MTD to 2100 MTD.
tial oxidation (POX). ATR and POX are
back time. - Partial oxidation burners for MDI, TDI
stand-alone processes, in which the
ATR is a vessel, normally operated and methanol plants (up to 600 MTD
hydrocarbon conversion is complet-
under pressure where in the top part in methanol)
ed, by means of Oxygen, inside one
the feedstock is mixed with oxygen - Autothermal reforming reactor for
reactor aided by internal combustion,
and steam by means of an “ad hoc” methanol and ammonia plants with
which supplies the heat necessary to
designed burner. In the combustion capacity ranging from 350 MTD to
make to the process happen.
chamber, partial combustion reac- 7000 MTD.
ATR with oxygen offers a simple and
tions take place, followed by methane
straight-forward process lay-out,
steam reforming reaction and shift The burner represents by far the most
where plot area and construction
conversion to equilibrium along the critical component in this kind of appli-
costs are reduced due to the compact
catalytic fixed bed placed downstream cation because it affects and governs
design and ultra – high capacity can
of the combustion chamber (see Fig- the process and the life cycle of the
easily be achieved with a single train
ure 1). unit under many aspects:
design.
The overall reaction is exothermic, re- - the composition at the outlet is af-
ATR is a game changer technology as
sulting in high outlet temperatures, fected not only by the process param-
it breaks the traditional upper capacity
typically 950-1100 °C. The pressure eters at the inlet of the unit, but also
limit of many plants being economical-

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by the fluid dynamics and the mixing 2. Detailed analysis of the most prom- The high velocity (which is a parameter
rate inside the vessel, all of which are ising solution is performed, using the of optimization) of the oxygen causes
governed by the burner’s design. As an most accurate models available, in- a controlled mixing between the two
example, an optimized ammonia sec- cluding CFD (Computational Fluid streams and reduces the flame length
ondary reformer’s burner can lead to a Dynamics) and in-house developed since the combustion reaction takes
substantially lower methane slip than chemical kinetic codes. Examples of place instantaneously after mixing,
with a standard burner, as is proven by CFD application to the design of an see Figure 4.
Casale references. ATR reactor are reported in Figures 3 The good level of mixing between oxy-
- In case of ATRs, an optimized burn- and 4. gen and feedstock achieved by Casale
er design is fundamental in guarantee- burners allows having an almost uni-
ing a long life of the catalyst and a con- 3. CFD is coupled with FEA (Finite Ele- form field of temperature, velocities
stant pressure drop along the catalyst ment Analysis) for the optimization of and composition at catalytic bed en-
life, thanks to an almost uniform inlet the burner geometry to provide long trance, thus allowing for a uniform uti-
temperature in the catalytic bed. and safe operating life of the equip- lization of the catalytic mass and low
- The burner is also the component ment. The data obtained from CFD and methane slip.
of the unit most likely to fail as it op- FEA is also fundamental to the selec- A short flame also avoids impingement
erates under extremely harsh condi- tion of the material in relation to ther- on the catalyst that can destroy its top
tions, therefore a good design is vital mal stresses, fatigue resistance and layer, with consequent performance
in order to avoid an unplanned plant metal dusting consideration. decrease and high-pressure drop. In
shut-down due to burner failure and to order to maximize the distance be-
make it as robust as possible against 4. Verification of the final solution for tween the flame and the catalyst sur-
potential mis-operations. soot formation, if required, with de- face, while maintaining reasonable di-
- An optimized burner design guar- tailed kinetic schemes for soot and mensions for the ATR reactor, the neck
antees soot-free operation at various soot precursors formation. of the “bottle shaped” vessel is used
plant loads, also with a fluctuating as a combustion chamber.
composition of the feed gas and with In the design phase steps 2, 3 and
“difficult” fuels. Soot-free operation is 4 are repeated until all the required The fluid-dynamic field inside the com-
very important as it avoids having soot burner design parameters are met or bustion chamber is designed in order
deposition on the catalyst or along the exceeded, always guaranteeing a low to protect the refractory lining from
pipelines and avoids the installation risk strategy for the implementation of the high temperature core of the flame
and operation of a soot abatement new ideas. (see Figure 2 and 3), preventing hot
unit altogether. spots on the refractory surface. The
overall shape of the fluid dynamic field
Being such an important component, 2. CASALE AUTOTHERMAL inside the combustion chamber is de-
the development cycle of a burner at
Casale is the focus of much attention
REFORMER REACTORS signed to be practically independent
from the plant load in order to allow a
in order to blend together the experi- turn down ratio as low as 30% of the
The combustion chamber design
ence and the lessons learnt from the design capacity.
adopted by Casale for its ATR reactors
past with new ideas, using the latest The burner is the key element of the
is conceptually very simple (see Figure
technological tools in order to always oxygen-fired reformer. Its goal is a con-
1). The oxygen stream is introduced
offer a state of the art burner. trolled mixing of the hydrocarbon and
at high velocity axially at the top of
oxygen feed stocks. Careful design of
the cylindrical combustion chamber
The development cycle of a burner/ the burner nozzles ensures a flow pat-
obtained in the “neck” of the “bottle
reactor for syngas production usually tern with efficient mixing that protects
shaped” ATR vessel. The process gas is
comprises four steps, with reviews and the refractory and the burner from the
introduced from one side at the top of
cross checks of the results at the end hot flame core.
the cylindrical chamber, perpendicular
of each step: For added safety and to achieve a
to the reactor main axis.
long operating life, Casale burners
To reduce the non-uniformities intro-
1. Selection of the most suitable con- are provided with a water cooling sys-
duced by the asymmetric inlet of the
figuration with tools based on Casale tem derived from the well-proven sys-
process gas, the burner is provided
experience in the field. tem adopted in the more critical POX
with a distributor placed upstream of
applications. The cooling system is
the burner tip.

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designed to achieve the maximum Better equilibrium approach thanks to

cooling efficiency on every surface ex- the uniformity of the gas flow and tem-
posed to the flame thus allowing for perature at catalyst entrance.
a long and safe operating life of the Reduced number plant shutdowns re-
equipment. The water cooling system lated to burner failure.
of Casale burner is effective on all the Safe Operation and Long life of the
burner body, not only on the tip, pro- burner, thanks to the tip water cool-
viding an additional level of safety and ing system (up to 8 years of proven op-
fault tolerance for every possible unex- eration with a single burner, see Sec-
pected operating condition. tion 3).
Casale ATR burners with water-cooling
are in operation since 2001 always
and still providing very good process
performances, safe operation and
a total operating life far longer than Figure 1 ATR reactor configuration
competitors’ designs. Casale burners,
thanks to their cooling water system
and exceptional mechanical strength,
were able, in the past, to withstand
severe and unexpected conditions al-
ways maintaining mechanical integri-
ty, superior process performances and
total safety.
ATR walls are built adopting a con-
ventional multi-layer refractory lining
design to protect the pressure ves-
sel from the hot gases in the reform-
er. This kind of design has hundreds of
references worldwide.

The main features of CASALE design

for the pure oxygen autothermal re-
former can be summarized as:

Good mixing between oxygen and feed-

stock, with an almost uniform field of
temperature, velocities and composi-
tion at catalytic bed entrance.
Low temperature of the reformer re-
fractory lining.
Water-cooled burner tip in order to en-
sure several years of safe operating
life with low temperature of the burner
surfaces exposed to the flame.
High flexibility in operation, allowing
running the burner with good perfor-
mances in a wide range of flow rates.

The above features lead to several im-

portant advantages over competitors’
design. The main advantages include:

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3. CASALE ATR BURNERS’

OPERATING EXPERIENCE
Casale has acquired a strong
experience in the design of ATR reactor
for the production of both methanol
and ammonia in two-step reforming
and pure ATR (with Coke Oven Gas -
COG) configurations.

Casale has several referenced

ATR reactors for the production of
methanol in operation or scheduled
for start-up, with capacities ranging
from 350 to 1350 MTD. Casale has
also completed the design of an ATR
reactor for a 7000 MTD two-step
reforming methanol plant.

Figure 3 Contours of Temperature in a typical

ATR reactor based on Casale design.

Figure 2 Stream lines in a typical ATR reactor

based on Casale design.

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Casale has also ATR reactors up in October 2001 (see Figures 4

references for the production of and 5). The methane slip and process
ammonia, the largest unit of which condition at the ATR reactor outlet are
being a COG based pure ATR of 1100 as per design even after more than
MTD capacity. nine years of operation with the same
burner (see Figure 5). The burner was
Figure 3 Contours of Temperature in a typical The first Casale ATR application was operated in a wide range of flow rates,
ATR reactor based on Casale design. for a two-step reforming 350 MTD from 20% to 110% of the design load,
methanol plant. This unit has been without performance losses or any
operating continuously since its start- other operational problem.

The largest Casale ATR reactor in

operation is installed in a two-step
reforming 1350 MTD methanol plant.
The unit was started-up in May 2004
(see Figure 6), and is operating since
then without any mechanical or
process issue.
The burner is usually operated in a
wide range of flow rates, from 30%
to 115% of the design load, always
providing performances according
to expectation in terms of pressure
drops and methane slip.
The regular turn around inspections
of the ATR reactor allowed for the
verification of the effectiveness of
the cooling water system installed
in the burner tip. After several years
of operation at high temperatures,
the penetrant liquid test showed no
traces of thermal fatigue cracks on
the burner tip, as shown in Figure 7.
The good conditions of the burner
tip and the absence of cracks can be
ascribed to both the efficient cooling
provided by the cooling water system
and the accurate fluid dynamic design
of the combustion chamber.
The ATR reactor turn-around
inspections also showed no
evidence of flame impingement on
the combustion chamber/vessel
refractory lining or on the target bricks
installed on top of the catalytic bed.
No traces of catalyst sintering or ruby
formation were evidenced during
catalyst replacements.

Similar operating records are common

to all Casale ATR burners.

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Figure 4. 350 MTD two-step reforming

methanol plant ATR burner installation.

Figure 5. Same burner as in Figure 2 after

extended operation.

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4. CONCLUSIONS
With a dozen units in successful
operation or under construction,
Casale has a strong background in the
design of oxygen ATR reactors for the
production syngas for both two-step
reforming and as stand-alone units.

The main features of the Casale ATR

design can be summarized as follows:

. Good mixing between oxygen and

feedstock, with an almost uniform
field of temperature, velocities and
composition at catalytic bed entrance,
i.e. better equilibrium approach thanks
to the uniformity of the gas flow and
temperature at catalyst entrance and
long catalyst life.
. Soot-free operation.
. Low temperature of the reformer
refractory lining.
Figure 6. 1350 MTD two-step reforming . Water-cooled burner tip in order to
methanol plant ATR burner before installa- ensure several years of safe operating
tion in May 2004.
life (more than 8 years already
reached with a single burner) with low
Figure 7. Same burner as in Figure 6. Liquid
temperature of the burner surfaces
penetrant test after several years of opera- exposed to the flame.
tion. . High flexibility in operation, allowing
running the burner with good
performances in a wide range of flow
rates.

Thanks to its experience in the

field, Casale is ready to successfully
address all the challenges in the
future market of syngas production
through Autothermal Reforming,
in order to provide the most cost
effective solutions both for new plants
and revamping of old plants.

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