Latest Casale Technologies for

Grass-roots Methanol plants

by
Massimo Iob
Methanol Casale SA

presented at
th
4 Methanol Markets & Tech,
Doha, Qatar, 17-18 February 2009

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 Latest Casale Technologies
for Grass-roots Methanol Plants
by
Massimo Iob
Methanol Casale SA

Abstract
The founding company of the Casale group, Ammonia Casale, has long been active in designing
grass-roots ammonia plants, mainly in the first half of the last century.

Since the end of the 70’s, the Casale group has gained a worldwide reputation for the revamping of
existing ammonia, urea and methanol plants of any kind gaining a leading position in this kind of
activity.

More recently Casale has developed advanced technologies for the design of grass-root ammonia,
urea and methanol plants, according to which grass-root plants have been designed.

This paper gives an overview of Casale’s technologies in the Methanol Field, highlighting their
most significant features and advantages.

The paper presents also the applications of these technologies, showing the role Casale can play
being able to supply advanced designs for grass-root methanol plants.

6900 Lugano
Switzerland,
Viawith
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 Content
1. Foreword

2. Technologies for grass-roots methanol plants

• Casale Standard Methanol Process

- Overview
- Characterizing Elements
- Performances

• Advances Methanol Process for large capacities

3. Implementation of projects for grass-roots plants

4. Conclusions

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 FOREWORD
Ammonia Casale S.A. is one of the oldest companies active in the field of synthetic ammonia
production, having been established in Lugano (Switzerland) in 1921 for the industrial development
and commercialization of Dr Luigi Casale’s inventions for the catalytic synthesis of ammonia.

Since the very beginning, and for many years now, Ammonia Casale has been active in the
construction of new plants, with over 200 such plants built worldwide.

Methanol Casale S.A. is a sister company of Ammonia Casale S.A. established in 1994 to restart
Casale activities in the methanol technology field.
At the beginning, the Methanol Casale activities concentrated on revamping synthesis reactors,
taking also advantage of the know-how gained by Ammonia Casale in reactor design, and soon
becoming a leader in the design of methanol synthesis reactors.

The main strength of Casale lies in the licensing of its technologies. Most of the technologies are
developed in house by a team of very specialized and experienced people.
Thanks to the innovative trend set by founder Dr Luigi Casale, plus the heritage and background of
subsequent management teams, Casale invested significantly in technology.

During the last decades this discipline evolved from an empirical art with an intuitive sense for
good design into a more rationalized activity.

Process design is now supported by sound insight into the chemistry of the processes, catalyst
behaviors, kinetic data, heat and mass transfer phenomena, fluid mechanics, science of
construction materials, and cost analysis.

Casale Technical Services avail themselves of specialists in all the above fields, as well as of
sophisticated tools for investigating, analyzing and picturing complex phenomena in a way
unachievable with ordinary skilled manual calculations. The process design is based on advanced
computer-aided techniques with applications ranging from process flow-sheeting to kinetics, to fluid
dynamics simulations and mechanical stress analysis.

Casale has been, in the last decades, very active in revamping existing plant and has extensive
experience in the design and implementation of complete plant revamping projects, including major
modifications to key equipment.

Casale’s plant revamp strategy has always been to develop and apply new, advanced
technologies to obtain the best possible improvement in plant performance at the minimum cost;
with the aim of reducing the energy consumption and/or increasing the capacity.

With the same strategy Casale has also developed, as a natural evolution of its revamping activity;
new technologies for grass-roots methanol plants. This paper will present these technologies
highlighting their features and some applications.

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 TECHNOLOGIES FOR NEW GRASS-ROOT METHANOL PLANTS
The Casale group can also offer very efficient designs for the construction of grass-roots methanol
plants through its company Methanol Casale.

For plant capacities up to 3000, Casale proposes its Standard process, while for capacities higher
than 3000 MTD and up to 7000-10000 Casale designs the plant according to its Advanced
Methanol process.

In the next sections, the two above mentioned processes are described.

The Standard Methanol process - Overview

The Casale Standard process for natural gas based methanol plants is based on the classical
steam reforming route.

The main process steps are, as shown in fig.10:

• Steam Reforming
• Heat recovery and cooling
• Compression
• Ammonia Synthesis
• Distillation

Fig. 1 - Casale Standard Methanol process

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 Casale Standard Methanol Process –Characterizing Elements
The main characterizing element of the Casale process is the synthesis converter. The synthesis
converter plays, in fact, a very important role in a methanol process as the synthesis loop
represent a significant part of the entire plant and the efficiency of the converter has a big influence
on the size of the loop.

The synthesis converter in the Casale process is designed according to its most advanced
methanol converter design which is the IMC, see fig 2 and 3.

The IMC is a pseudo isothermal converter in which the heat transfer surfaces are plates instead of
tubes, and the catalyst is outside the cooling plates.
The new design has been applied for the first time in a methanol synthesis converter in 2002.

Fig. 2 - Cooling Plate Fig. 3 - IMC converter

This new design has the following main characteristics:

• The heat removal from different parts of the catalytic bed can be controlled independently
enabling a perfect control the temperature profile in the catalyst mass so that it becomes
possible to operate the catalyst according to the highest reaction rate temperature profile
• Heat can be removed directly from the catalytic bed without the need of tube sheets
• The catalyst bed is continuous, supported by a layer of inert material, so it can be easily
loaded from the top and unloaded from the bottom, through drop-out pipes
• The converter can be designed with Casale axial-radial flow configuration

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 Thanks to the above features, it is possible to reach the maximum efficiency for given operating
conditions and reaction volume and to minimize the size and number of the loop equipment and
pipes and the energy consumption and to maximize the carbon efficiency.

Alternative configurations of IMC can be designed, since the flow path can be axial or axial-
radial, while the cooling fluid flowing inside the plates can be the fresh converter feed gas, water or
other heat transfer fluid. A combination of different fluid is also possible.

- Axial Gas-Cooled Converter

The plates are in immersed in the catalyst bed, a

cooling fluid, in this case the fresh synthesis gas enters
from a nozzle on the top and is distributed to the
plates. Inside the plates the gas flows downward, i.e.
co-current with the gas in the catalyst bed. The fresh
syngas in the plate is in this way preheated up to the
reaction temperature, and can then be collected to a
central raiser pipe, from where it reaches the top of the
catalyst bed. There the gas enters the bed flowing
downward, reacting to form methanol, and releasing
heat to the plates.
After crossing the catalyst bed the reacted gas exits
from the bottom central nozzle.

The first axial gas cooled IMC is on stream since 2002

in a plant in Russia

Fig. 4 - axial gas-cooled IMC

- Axial-radial Gas-Cooled Converter

Casale Axial-Radial technology, already very

common in ammonia plants, can be applied also for the
design of methanol converter.
In an axial-radial catalyst bed (see Fig. 5) most (about
90%) of the gas passes through the catalyst bed in a
radial direction, resulting in very low pressure drop.
The balance passes down through a top layer of
catalyst in an axial direction, thus eliminating the need
for a top cover on the catalyst bed.
This layout overcomes the main drawback of axial
design, specifically the limitation in the maximum
capacity that can be reached in a single converter, due
to the high pressure drop across the bed.
The essential advantages of the axial-radial catalyst
bed concept are essentially:
• low pressure drop;
• full utilization of catalyst installed
Fig 5 - Axial-Radial bed

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 High efficiency and low pressure drop are important features to minimize equipment size and
energy consumption.

Another advantage of the above features is that with the IMC design it is possible to build
converters which have a very high capacity in a single vessel.

Figure 6 illustrates the configuration of an axial-radial plate

cooled converter.

The first axial-radial gas cooled converter is on stream

since 2006 in the AMPCO plant in Equatorial Guinea.

The AMPCO converter has been revamped with the ‘in-

situ’ technology, i.e. re-utilizing the pressure vessel in
which new internals are installed during a turnaround. Also
this revamping has been done within a capacity increase
projects.

The converter was originally a four-bed three-quenches

design, and, without modifying the pressure vessel, it has
been revamped to a new configuration featuring two axial-
radial beds, each one gas cooled with plates.

- Steam Raising IMC Fig 6 - Axial-Radial gas-

cooled IMC
Another configuration of the plate cooled converter is
obtained when boiling water is flowing inside the plates.
Also in this case there is no tubesheet, therefore there is no constraint in the converter size,
and the construction is light, consisting of a normal pressure vessel containing the catalyst bed
and the plates
The plates are dimpled, obtained in an automatic production process, having a very high
quality consistency, where the manual input is minimal.
The plates are surrounded by the catalyst mass where the process gas is flowing. The process
gas flow can be axial or axial-radial.

The advantage of the plate-cooled steam-raising design is to overcome the traditional

limitations, allowing much higher production rates in a single converter, to introduce a new
concept in reliability and catalyst handling, and to allow a better temperature control in the
catalyst mass, increasing the operating life of the catalyst charge.

This design has been applied for the first time in 2006 in the Metafrax plant in Gubakha,
Russia, in a revamping aimed at capacity increase.

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 Fig 7 - Axial Steam Raising Fig 8 – Axial-radial Steam
IMC Raising IMC

Casale Standard Methanol Process – Performances

Thanks to those characterizing elements, whose features have been explained in the previous
sections, the Casale Standard Methanol process has very outstanding performances, which makes
it possible to reduce, for a given capacity, the size of the equipment and, therefore, to build a plant
with lower investment costs then with other processes :
• Steam to carbon ratio (referred to NG stream only): 2.5 to 3.0
• Methanol loop pressure: 80 bar
• Methanol conversion: ab 7 %
• Energy consumptions: ab. 7 Gcal/MT of produced methanol

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 The Advanced Methanol Process for Large Capacity
The Casale Advanced Methanol process has been developed by Casale for the design of natural
gas based single line methanol plants with very high capacities, up to 7000 MTD and more.

The main concept of the Casale Advanced Methanol process is to use Combined Reforming
scheme (or Banquy scheme) to generate the syngas in large quantity, and to use the Casale IMC
converter able to produce very high capacity with a single vessel design.

As illustrated in fig 9 the Casale Advanced Methanol process comprises the following main steps:
• Air Separation (ASU)
• Steam Reforming
• Autothermal Reforming (ATR)
• Heat recovery and cooling
• Compression
• Methanol Synthesis
• Distillation

Fig. 9 - Casale Advanced Methanol Process

The proposed plant scheme is based on the production of synthesis gas from natural gas with the
well known combined reforming scheme, also known as the Banquy scheme, which is the
combination of a steam reforming with an auto thermal reforming (ATR) with oxygen.
According to this scheme, the natural gas feed is divided into two fractions, a first fraction is sent to
the steam reforming while the second by-passes the steam reforming and is sent straight to the
ATR converter, together with the effluent from the steam reforming, where it reacts with Oxygen,
produced by an Air Separation Unit, to generate the syngas with a composition suitable for the
methanol production.

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 Pre-reforming Reactor technology

Depending on the size of the plant, the installation of a pre-reforming unit can be provided in order
to minimize the dimensions of the reformer.
The pre-reforming reactor proposed by METHANOL CASALE is designed according to the axial-
radial technology for catalyst beds (see Fig. 10 and Fig. 11).

Fig. 10 - Axial-radial Bed, Gas Distribution Fig. 11- Axial Radial Pre-Reformer

The advantages of using this technology for pre-reforming reactors are:

• the low pressure drop achievable;
• the use of small size catalyst;
• the lower operating temperature of the vessel wall when the reaction is exothermic.

The small-size catalyst has two advantages in comparison with the large-size one:
• a higher sulfur pick-up, that means a longer life since sulfur is the main poison;
• a higher activity.
This means that, with respect to the larger size catalyst, it is possible to reduce the catalyst volume
to have the same life or with the same volume to have a longer life. The lower operating
temperature of the vessel wall is due to the fact that the feed gas is colder than the product one, in
case of exothermic reaction, and this helps to avoid metallurgical problems due to the high
operating temperatures.
Regarding the operation of an axial-radial pre-reformer it is to be noted that the temperature profile
in the catalyst bed can be measured and followed easily, thanks to the presence of thermocouples
in different position along the radial direction in the bed. Also catalyst loading and unloading is
very easy, as the axial-radial bed is completely open on the top granting an easy access to the bed

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 even for small diameter vessels, while for unloading there are drop out pipes provided at the
bottom.
The utilization of this reactor allows carrying out part of the primary reforming reaction (about 10-
15%) outside the primary reformer, allowing to increase the capacity of existing unit, as well as to
reduce the size of reformer to be implemented in new plants.
Another advantage of the pre-reformer is that it transforms all higher hydrocarbons to methane,
and performing part of the reforming reactions, produces some hydrogen. These two actions allow
increasing the preheating temperature of the process gas, and also the reduction of the steam
carbon ratio, therefore reducing the energy consumption of the primary reforming section.

The first axial-radial pre-reformer was installed in 2000 in Brazil, while three more were installed
later.

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 Auto-Thermal Reformer Technology

The ATR is characterized by a special Casale design to achieve a perfect

mixing between oxygen and gas obtaining a very good combustion.
The combustion chamber design of the Casale ATR unit is conceptually
very simple. The oxygen stream is introduced at a high velocity axially at
the top of the combustion cylindrical chamber. The process gas is
introduced from one side at the top of the cylindrical chamber, before the
burner tip.
The high velocity of the oxygen increases mixing between the two and
reduces the flame length since the combustion reaction takes place
instantaneously after mixing. A short flame avoids impingement on the
catalyst surface that would result in destroying its top layer with
consequent performance decrease and high-pressure drop.
The fluid-dynamic field inside the combustion chamber is designed in
order to protect the refractory lining from the high temperature core of the Fig. 12 – ATR
flame, preventing hot spots on the lining surface. burner
The burner is provided with a water-cooling system derived from the well-proven system adopted
in the more demanding POX burner Casale design.

This design, which is in service in few methanol and ammonia plants, has the following features:
• High reliability and long durability, with several years of operation without any sign of
deterioration.
• High efficiency of conversion of methane to syngas, thanks to the more uniform field of
temperature and composition;
• Longer lasting performances of the catalyst, thanks to the short flame length avoiding
impingement and damages on catalyst surface;
• Total absence of soot formation, as evidenced by the analysis and inspections on ATR
catalyst and downstream equipment;
• Wide flexibility, it has been successfully operated at temperature conditions,
composition and flow rates far from the design ones.
The first unit of the Casale ATR was put in service since November 2001 in a Methanol plant in
China, for the production of synthesis gas. The above picture (fig. 12) was taken during burner
installation. Since then several others have been installed or are under construction.
The syngas produced from the combined reforming section is sent, after heat recovery, cooling
and compression, to the synthesis section.

The Methanol Synthesis section is based on the IMC design described in the previous section.
The methanol converter has a two beds configuration; with one bed using fresh converter feed gas
as cooling media, and the other using boiling water.
The very efficient IMC design, combined with the special converter configuration, enables to reach
very large capacity of the synthesis loop with a still feasible size of its equipment.

The produced methanol is purified in a fairly standard three-column distillation system.

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 Advanced Methanol Process – Performances

Thanks to its innovative and novel design and to its special features, which have been explained
in the previous section, the Advanced Methanol process has very outstanding performances, such
as a very low total energy consumptions: ab. 6.8 Gcal/MT of produced methanol.

These outstanding performances make it feasible to build plants with very large capacity, 7000
MTD and higher, in a real single line.

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 IMPLEMENTATION OF PROJECTS FOR GRASS-ROOTS PLANTS

The Casale Standard methanol process is currently operating in two plants in Russia designed for
a capacity of 1350 MTD and 1650 MTD respectively.

The plants that have been designed by Casale, who supplied also all engineering and most of the
material on EP basis, are in operation since 2000 and 2006 respectively.

A 7000 MTD plant designed according to the Casale Advanced methanol process is under
implementation in Iran.

Key components of Casale methanol processes, such as the IMC converter, are in operation at
capacities up to 3200 MTD.

Fig. 13
Casale Standard
methanol plant in
Operation in Russia

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 CONCLUSIONS
Through the continuous development of its technologies, Casale has been able to develop
innovative processes for methanol grass-roots plants.

With these new processes Casale can design world scale methanol plants and is ready to respond
to the future market demand in terms of plant capacity with its advanced processes specially
conceived to design plants of very large capacity.

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