SCIENCE &

TECHNOLOGY
Raffaele Ostuni
Research & Technology
Development Department
Methanol Casale S.A.
Lugano (Svizzera)
[email protected]

Grass-roots Casale methanol plant

DISTINCTIVE TECHNOLOGIES
FOR METHANOL PLANTS
The Casale Group has a worldwide reputation as the leader in the revamping of existing fertilizer and methanol plants of any kind.
More recently, Casale has applied its advanced technologies also to the design of new grass-roots methanol plants with capacity
up to 7,000 t/d in a single train. This paper provides an overview of Casales most distinctive technologies in the methanol field,
their application to new methanol plants, and their prominent role in the trend to ever larger single-train plant capacities.

Casale background leader in the design of methanol synthesis reactors.

The Casale Group has been active in technology development and As it has gained experience, Methanol Casale has also become a
engineering since 1921, when Dr. Luigi Casale developed one of the leader in revamping complete methanol plants and in designing new
first processes for the synthetic production of ammonia, and founded ones. Key achievements in plant upgrading include capacity increase,
Ammonia Casale. Over the years, the company has diversified and reduced specific consumption, and improvement in the quality of the
presently the Casale Group is formed of four companies (Ammonia raw methanol. Methanol Casale has also recently designed grass-
Casale, Urea Casale, Methanol Casale and Casale Chemicals), offer- roots plants, including the worlds largest plant with a capacity of
ing its services in the fields of ammonia, urea, methanol and deriva- 7,000 t/d, most of which are already in operation.
tives production. From the very beginning, the success of the Group These plants incorporate Casales most advanced technologies, such
was linked to its ability to develop innovations and introduce them to as the IMC (Isothermal Methanol Converter). This is the ultimate step
the market. This trend has been preserved and nurtured as central to in terms of converter efficiency, which makes it possible to design very
the companys culture by subsequent management teams. large methanol units, with capacities of 7,000 t/d and more, in a real
Casale Groups innovative concepts have found wide acceptance in single train and with a single vessel converter. This paper presents
the market, making a great contribution to the progress of the ammo- Casale process design for large methanol plants using natural gas as
nia, urea and methanol industries. Methanol Casale was established in feedstock. Moreover, it focuses on the application of Casale technolo-
1994 to resume the activities in the methanol field and rapidly achieved gies in these plants, their distinctive features and their importance to
very successful breakthroughs. At the beginning, Methanol Casale increase single-train capacities, to lower capital and operating costs,
concentrated on revamping synthesis reactors and it soon became and to improve the plants operability and reliability.

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Casale process for large methanol plants natural gas consumption is lower than the pure reforming scheme.
A conceptual analysis of the main process steps involved in the syn- The Combined Reforming Process (shown in Fig. 2) combines the
thesis of methanol is important to understand the basis for Casales advantages of the two schemes outlined above, and it is the flow

SCIENCE & TECHNOLOGY

technology applied to large methanol plants. scheme adopted by Casale for the syngas generation in large
The production of methanol from natural gas includes three main sec- methanol plants.
tions: All the feed natural gas is pre-reformed. The pre-reformed feed is then
- synthesis gas generation split in two fractions, one sent to the steam reforming while the sec-
- raw methanol synthesis ond by-passes the steam reforming. An Auto-Thermal Reformer (ATR)
- methanol distillation. blown with oxygen from an Air Separation Unit (ASU) is installed down-
It is by optimizing the process scheme for each of these sections, and stream the primary reformer to process the reformer effluent and the
using its advanced technologies, that Casale can supply the largest by-pass. The syngas generated by this process is already balanced for
single-train methanol plants with best performances and highest relia- methanol synthesis. However, a HRU (Hydrogen Recovery Unit) is pro-
bility. The flowsheet of the Casale advanced methanol process is vided to further reduce the size of the primary reformer.
shown in Fig. 1. The Casale front-end scheme, based on the combined reforming con-
cept, features a smaller ASU than the pure ATR process, thanks to the
Synthesis gas generation lower oxygen consumption, and lower gas consumption. The primary
The first step to methanol production is the conversion of natural gas reformer is relatively small, and can be built as a single unit for plant
to a mixture of hydrogen and carbon oxides (syngas), either by catalyt- capacities higher than 7,000 t/d.
ic steam reforming, or by catalytic partial oxidation, or by a combina-
tion thereof. The three methods yield different qualities of syngas. Raw methanol synthesis
The methanol synthesis reaction requires that the amount of hydrogen The make-up gas is transformed into crude methanol in the synthesis
and carbon oxides in the syngas is properly balanced, to minimize the converter, which is the core of the methanol plant. The conversion of
consumption per unit methanol production rate. syngas to methanol is only partial, due to the equilibrium limitation,
In the Pure Steam Reforming Process, the syngas is generated only hence the reactor effluents must be recycled to the synthesis convert-
by reforming of natural gas with steam, according to the steam reform- er along with fresh make-up gas after separation of the raw methanol
ing and shift reactions. product.
The pure reforming process yields a
H2-rich syngas, therefore not suited for
methanol synthesis unless a stream of
CO2 is available to balance it (which is
usually not the case).
This scheme is characterized by a large
steam reformer or multiple parallel
reformers if the capacity is higher than
2,500-3,000 t/d. Moreover, the excess
of H2 in this process route makes it
inefficient and unattractive for large
plants. The Pure Autothermal Reform-
ing Process generates the syngas by
partial oxidation of the feed with oxy- Fig. 1 - Advanced Casale methanol process
gen from an Air Separation Unit (ASU).
Opposite to the steam reforming route,
the syngas generated by the ATR
process is H2-poor: to adjust its com-
position, it is necessary to draw a rela-
tively large purge stream from the loop,
and treat it to recover its hydrogen con-
tent. The pure ATR scheme requires
much oxygen (about 0.7 t/t MeOH), to
be produced in a large ASU. The total Fig. 2 - Syngas generation by combined reforming

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 SCIENCE &
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the final purification is performed in two
steps: the topping column separates
the lighter compounds from the liquid
mixture, while the refining section pro-
vides the final separation of water and
higher ends from the pure product. The
refining section is split in two separated
columns, one under pressure and one
atmospheric, which is the arrangement
achieving the least distillation energy
consumption.
The arrangement of Casale three-col-
umn distillation is shown in Fig. 4.

Distinctive technologies
Fig. 3 - Casale synthesis loop
in large methanol plants
The Casale synthesis loop is very simple, as illustrated in Fig. 3. It fea- Casale has deeply optimized its methanol process scheme. However,
tures a single synthesis converter, a gas-gas exchanger to preheat the it is the application of its distinctive technologies that allows the out-
converter feed, a methanol condenser, a liquid methanol product sep- standing features of the methanol plant in the most efficient and reli-
arator, a hydrogen recovery unit from the purge gas, a syngas com- able way.
pressor and a circulating compressor. The Casale technologies applied in the new large methanol plants are
The core of the Casale synthesis loop is the IMC (Isothermal Methanol the Pre-Reformer, the Autothermal Reformer and the IMC Synthesis
Converter): this is the ultimate converter generation, which achieves a Converter, all described in this section of the paper.
very large methanol capacity with a single vessel converter.
The synthesis of methanol is exothermic, limited by the equilibrium. Pre-reforming reactor technology
The lower is the temperature, the more favorable the equilibrium Casales pre-reforming reactor is designed according to the axial-radi-
methanol concentration. On the other hand, high temperatures pro- al technology for catalyst beds, as shown in Fig. 5 and 6.
mote faster reaction kinetics.
An ideal converter follows the
maximum rate curve and
achieves the highest conver-
sion by removing the reaction
heat from the catalyst mass
at a controlled rate in the cat-
alyst bed. This is exactly what
the Casale IMC plate-cooled
converter does.
The Casale IMC synthesis
converter and synloop
achieve high syngas conver-
sion with low recycle ratio,
enabling a smaller size for the
loop items.

Distillation section
The crude methanol typically
needs to be purified to reach
the specification required by
the specific application.
To reach AA grade methanol, Fig. 4 - Casale three-column distillation

126 Lug./Ago. 11
 ing, poor distribution or deterioration. At the
same time, the gas pressure drop is low and
stable throughout the life of the catalyst.

SCIENCE & TECHNOLOGY

Another advantage of the axial-radial design,
specific for pre-reformers, is that the small-
size catalyst has higher sulphur resistance
and higher activity: as a consequence, the
catalyst volume is reduced for the same life,
with consequent cost saving.
The axial-radial pre-reformer is a distinctive
element in Casales scheme for new large
methanol plants, achieving several important
benefits.
The pre-reformer protects the plant against
coke formation in the primary reformer feed
preheat coil and catalyst tubes inlet, by
destroying the higher hydrocarbons con-
tained in the natural gas, stabilizing the feed
and avoiding coke formation upstream the
reformer and ATR: this increases the plant
Fig. 5 - Casale axial-radial catalyst bed Fig. 6 - Casale axial-radial Pre-Reformer
reliability. Moreover, steam reforming of the
The Casale axial-radial technology is extensively applied in ammonia feed partially occurs in the pre-reformer, thereby reducing the load on
and methanol plants, having been used in more than 500 (five hun- the primary reformer.
dred) catalyst beds. The pre-reformer also allows reducing the steam/carbon ratio, which
In an axial-radial catalyst bed as in Fig. 5, most of the gas crosses the lowers the energy consumption, and to increase the pre-heating tem-
catalyst bed in a radial direction, resulting in very low pressure drop. perature of the pre-reformed stream, with consequent further reduc-
The balance passes down through a top layer of catalyst in an axial tion of the radiant duty (and cost) of the primary reformer.
direction, thus eliminating the need for a top cover on the
catalyst bed.
This layout overcomes the main drawback of axial design,
i.e. 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 concept are:
- low pressure drop, stable with time and not controlled
by the catalyst bed;
- full utilization of catalyst volume installed;
- possibility to use small size catalyst, more active and
more resistant to poisons;
- lower operating temperature of the vessel wall, when
the reaction is exothermic (e.g. shift, methanol and
ammonia synthesis);
- possibility to design slim vessels, with important capital
cost saving especially when high grade construction
materials are required, and no size limitations.
Casale axial-radial design ensures a perfect gas distribu-
tion on the reacting side, controlled by perforated walls
(the inlet and outlet collectors). Since the gas distribution
is controlled by the walls and not by the catalyst bed, it is
not affected by the catalyst aging, catalyst uneven load- Fig. 7 - Casale ATR burner

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 SCIENCE &
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The first Casale axial-radial pre-reformer is successfully in operation flame, preventing hot spots on the lining surface.
since 2000 in a revamped plant in Brazil. Three more units were The burner is provided with a water-cooling system derived from the
installed in the following years, both in ammonia and methanol plants. well-proven system adopted in the more demanding Casale POX
burner. This design, which is in service in methanol and ammonia
Auto-Thermal Reformer Technology (ATR) plants, has the following features:
The ATR is characterized by a special Casale design to achieve a per- - high reliability and long durability, with several years of operation with
fect mixing between oxygen and gas, obtaining a very good combus- no deterioration;
tion. The combustion chamber design of the Casale ATR unit is con- - high efficiency of conversion of methane to syngas, thanks to the uni-
ceptually very simple. The oxygen stream is introduced at a high veloc- form field of temperature and composition;
ity axially at the top of the combustion cylindrical chamber. The - longer lasting performances of the catalyst, thanks to the short flame
process gas is introduced from one side at the top of the cylindrical length avoiding impingement and damages on catalyst surface;
chamber, before the burner tip. The high velocity of the oxygen - total absence of soot formation, as evidenced by the analysis and
increases mixing between the two and reduces the flame length since inspections on ATR catalyst and downstream equipment;
the combustion reaction takes place instantaneously after mixing. A - wide flexibility: it has been successfully operated at temperature con-
short flame avoids impingement on the catalyst surface that would ditions, composition and flow rates far from the design ones.
result in destroying its top layer with consequent performance The first unit of the Casale ATR was put in service since November
decrease and high-pressure drop. 2001 in a Methanol plant in China. The picture in Fig. 7 was taken dur-
The fluid-dynamic field inside the combustion chamber is designed to ing burner installation. Since then, several others have been installed
protect the refractory lining from the high temperature core of the or are under construction.
Isothermal Methanol Converter
(IMC) Synthesis Technology
The synthesis converter in the Casale
process is designed according to its
most advanced methanol converter
design: the IMC (see Fig. 8 and 9).
The IMC is a pseudo isothermal convert-
er in which the heat transfer surfaces are
plates, and the catalyst is loaded outside
the cooling plates. The Casale IMC
design was first applied to methanol syn-
thesis in 2002, and has achieved impor-
tant successes in the last ten years.
The IMC design has the following main
characteristics:
- the heat removal from different parts of
the catalytic bed can be adjusted inde-
pendently, enabling a perfect control the
temperature profile in the catalyst mass,
and operation of the converter 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, support-
ed by a layer of inert material, so it can be
easily loaded from the top and unloaded
from the bottom, through drop-out
pipes;
Fig. 8 - Casale IMC converter plates Fig. 9 - Casale axial-radial IMC converter - the converter can be designed with

128 Lug./Ago. 11
 Casale axial-radial flow configuration, to benefit of section of the plates. The plates distribution system is
the features of this superior technology. designed to achieve the desired distribution with any
Thanks to the above features, it is possible to reach operating condition. The Casale loop arrangement

SCIENCE & TECHNOLOGY

the maximum efficiency for given operating condi- proposed for large capacity methanol plants features
tions and reaction volume, to minimize the size and a single, axial- radial, steam generating converter,
number of the loop equipment and pipes, and opti- entailing two major benefits: the reaction heat is
mize the energy consumption and size of the front- entirely recovered to generate steam, maximizing the
end. The construction of the converter internals is synloop heat recovery, and the gas only crosses one
conceived so that there is no tubesheet, therefore axial-radial catalyst bed, therefore the converter pres-
there is no constraint in the converter size, and the sure drop is well below 1 bar. Another advantage of
construction is light, consisting of a normal pressure the Casale synloop is that, since the converter diam-
vessel containing the catalyst bed and the plates. eter is only marginally influenced by the circulation (at
The plates are obtained in an automatic production a given capacity and make-up condition), the loop
process consisting in their welding with a laser con- recycle ratio can be optimized to maintain a low syn-
trolled by a computer. This results in a very high qual- gas consumption both with fresh catalyst (SOR) and
ity consistency, where the manual input is minimal. spent catalyst (EOR). Other designs with axial con-
The advantage of the IMC design is to overcome the verters, instead, are forced to use low recycle ratios
traditional limitations, allowing much higher produc- to contain the vessels size, and may suffer a penalty
tion rates in a single converter, to introduce a new in capacity at EOR.
concept in reliability and catalyst handling, and to
allow a better temperature control in the catalyst Conclusions
mass, increasing the operating life of the catalyst Thanks to its innovative design and its distinctive
charge. Alternative configurations of IMC can be technologies, the Casale Advanced Methanol
designed, since the flow path can be axial or axial- process has outstanding performances, such as a
radial, while the cooling fluid flowing inside the plates total energy consumption lower than 6.7 Gcal/MT of
can be the fresh converter feed gas, water or other produced methanol (including the ASU).
heat transfer fluid. A combination of different fluid is The efficiency of the plant is also reflected in the min-
also possible. imum consumption and size of the utilities plant, par-
For large methanol plants, the most suitable type of Fig. 10 - Casale IMC ticularly the cooling towers. Another important feature
IMC converter is the axial-radial converter, with boil- for large methanol plants of the Casale scheme is that the size of all the main
ing boiler feed water inside the plates, such as the picture shown in plant items is not critical for the construction and/or the supply of a
Fig. 10. The bed is axial-radial. Several plate-shaped heat exchangers plant with capacity of 7,000 t/d or more, especially as regards the
are dipped in the catalyst mass, in multiple rounds, and crossed by steam reformer, the Air Separation unit and the syngas compressor.
water, which is heated at the expense of the reaction side generating With Casale IMC design, even more than 10,000 t/d can be achieved
medium pressure steam (approximately 25-35 bar). A pump circulates in a single pressure vessel. These outstanding features of the Casale
the water/steam mixture through the cooling plates. technology make it economically attractive to build plants with very
The catalyst temperature is controlled by changing the saturated large capacity, 7,000 t/d and higher, in a real single line.
steam pressure according to the process requirements (i.e. catalyst Through the continuous development of its technologies, Casale has
deactivation). been able to develop innovative processes for methanol grass-roots
The fluid in the plates is boiling water, flowing axially. Since the water plants. Casale is ready to respond to the future market demand with
is saturated, there is no concern about cross-flow between gas side its advanced process and technologies, specially conceived for plants
and cooling side, as the water-steam temperature is the same in every with very large capacity.

RIASSUNTO
Tecnologie proprietarie per gli impianti di sintesi di metanolo
Il Gruppo Casale leader mondiale nellambito della modernizzazione dimpianti per la sintesi di metanolo e fertilizzanti, grazie all'applicazione di conoscenze
specifiche e tecnologie proprietarie. Recentemente, Casale ha applicato queste tecnologie anche alla progettazione di nuove unit, tra cui limpianto di sintesi
metanolo di maggior capacit al mondo, da 7.000 t/d. Larticolo descrive le principali tecnologie del Gruppo Casale applicate alla sintesi del metanolo, eviden-
ziandone il ruolo primario nel consentire la costruzione dimpianti di taglia sempre maggiore, per seguire le esigenze di questo particolare mercato.

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