methanol process

m3000tm - M7000tm - M2000ctm

Optimized processes
for any plant size
and feedstock
 casale methanol process M3000tm - M7000tm - M2000ctm

methanol process AIR oxygen

3 columns
asu methanol
distillation

CH4
HEAT condensation
STEAM SYNGAS imc
atr RECOVERY &
M3000 and M7000 are Casale's processes for natural gas-based methanol plants.
™ ™ REFORMER
& cooling
COMPRESSOR converter
separation

M3000™ is used for plants having a capacity ranging from 1,000 to 3,000 MTD, and is optimized in order to
reduce the investment cost and the energy consumption.
M7000™ is used for plants having a capacity ranging from 3,000 to 7,000 MTD, and is optimized to reach very fuel
large capacities in the most efficient possible way. HRU

M2000C™ is Casale's process for coal-based methanol plants with capacity ranging from 1,000 to 2,500 MTD.
The main difference between the three processes is the way the synthesis gas is generated. Main steps of M7000TM process

KEY FEATURES OF CASALE METHANOL PROCESSES

• Best design for any feedstock A further feature, which reduces the duty on both the primary reformer and the ATR, is a pre-reformer, through which all of
• Real single-line very large plants (more than 10’000 MTD with a single reactor) the natural gas feed is routed after desulfurization. The pre-reformed feed is then split into two fractions; one is sent to the
• Low steam to carbon ratio primary reformer and then on to the ATR, the other directly to the ATR.
• Low energy consumption, less than 7.0 Gcal/MT for M3000TM and less than 6.7 Gkal/MT for M7000TM This process can produce synthesis gas that is correctly balanced for methanol synthesis, but a hydrogen recovery unit
• Optimized plant cost (HRU) is still provided, allowing the size of the primary reformer to be reduced further. Thus a single reforming furnace of
manageable proportions can serve a 7,000-t/d plant.
Clearly, because the ATR is only handling part of the reforming duty, its oxygen requirement is smaller than that of a purely
ATR installation, so the ASU is proportionately smaller, too.

m7000tm process outline

Synthesis gas generation ng
pre primary SYNtesis
atr
The capacity limit on a single steam reforming furnace is about 3,000 t/d of methanol. Duplicating REFORMER REFORMER GAS
reforming furnaces is an expensive option, particularly as they would still be producing a non-ideal
synthesis gas.
Casale has therefore adopted a combination of primary and autothermal reforming, which optimizes steam

the combination of energy consumption, stoichiometric number and plant cost. o2

Combined reforming syngas generation

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 casale methanol process M3000tm - M7000tm - M2000ctm

purge gas
hydrogen
recovery
unit

H2
separator
meoh
condenser
m3000tm process outline
casale Synthesis gas generation
m.u. syngas gas-gas
circulator imc
gas exchanger
compressor converter In this case the generation of synthesis gas is obtained with a steam reformer only, thanks to the lower production rate requi-
red. As in the M7000™ process, the desulfurized natural gas, mixed with steam, is first preheated in a coil in the convection
section of the primary reformer and then passed through a pre-reformer. The pre-reformed gas is further pre-heated in the
convection section before entering the reformer tubes. To minimize the plant’s overall gas consumption the steam-to-carbon
methanol synthesis loop mp ratio is set at 2.5-3.0.
steam
The Casale synthesis loop is very simple. It features a single synthesis converter, a gas-gas exchanger to preheat The hot gas leaving the reformer is then routed to a train of exchangers to recover its heat value, while the process condensate
the converter feed and cool the converter effluent, a methanol condenser, a liquid methanol product separator,
is separated and sent to a steam stripper.
a purge gas HRU, a syngas compressor and a circulating compressor.
The syngas and circulating compressor can be supplied as separate machines, or as different barrels on the same shaft, depending on the Synthesis gas generated in the M3000™ process has a large H2 excess with respect to methanol synthesis. If CO2 is availa-
plant size and specific client requirements. The heart of the synthesis loop is the Casale IMC (Isothermal Methanol Converter), in which the ble, then the synthesis gas composition can be adjusted as required.
heat of reaction is removed by means of a set of heat exchanging plates embedded in the catalyst,
either preheating the incoming gas or boiler feed water or raising steam. Thanks to the optimized reforming conditions, the use of a pre-reformer to lower the amount of steam in the process gas, and
The internal cooling system of the IMC converter is more efficient and more maintenance-friendly than in other designs such as, for instance, the highly efficient IMC converter in the synthesis loop, a smaller primary reformer can be used than in rival processes. It can
the old tube-cooled converters, even in very large units.
be built as a single unit for plant capacities of about 3,000 t/d.
Because of the high per-pass conversion rates attained in the Casale IMC synthesis converter and synthesis loop, the rate of gas recycle is
proportionately lower, enabling equipment sizes in the loop to be reduced.

Distillation section
To reach AA grade methanol, the final purification is performed by a two-step distillation: the topping column separates the lighter compoun-
ds, while the refining section provides the final separation of water and higher ends from the pure product.
3 columns
methanol
The refining section comprises two separate columns, one under pressure, the other atmospheric, which is the arrangement that consumes distillation
least distillation energy.
refining CH4
topping section
off gas
section

raw meoh HEAT condensation

STEAM SYNGAS imc
atr RECOVERY &
REFORMER COMPRESSOR converter
& cooling separation

Process fuel
gas refined meho

fueL oil

Process gas steam Main steps of M3000™ process

boiler

bottom water

Hp column lp column
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 casale methanol process M3000tm - M7000tm - M2000ctm

Raw methanol synthesis Synthesis gas work-up

The methanol synthesis is fundamentally similar to that of the M7000™ process, except there is no need for an HRU since the gas is already The raw syngas generated in a coal gasification based plant contains much carbon monoxide, a portion of which has to be converted
rich in hydrogen. to hydrogen to yield a more balanced gas for methanol synthesis.
The methanol synthesis loop is designed once again around the Casale IMC plate-cooled synthesis converter. In spite of the excess of One or two shift converters are usually installed for this purpose, downstream of the coal gasifier. These are designed to operate on the raw synthesis
hydrogen in the synthesis gas, with the Casale IMC technology it is never necessary to have more than one converter vessel, which keeps the gas before it has been subjected to any treatment to remove its sulfur content and surplus carbon dioxide. In compensation
synthesis loop arrangement simple with the minimum number of pieces of equipment. for the excess of carbon and the high CO content, synthesis gas from coal gasification has a very low concentration of inerts.
Because of the high conversion per pass in the IMC, it is possible to operate at a relatively low loop pressure (80 bar), reducing the duty on the In addition to these, the make-up gas typically contains trace elements, such as sulfur and arsenic. These compounds are normally washed away
synthesis gas compressor. in the gas treatment upstream the synthesis loop (Rectisol), but there may be problems due to upset, maloperation or underperformance of some
Another outstanding advantage of the IMC is the very low pressure drop (less than 1 bar), which is attributable to the axial-radial flow treatment units that may leave undesirable levels of impurities in the gas.
configuration of the catalyst bed. With the minimal number of pieces of equipment in the synthesis loop, this makes the overall loop pressure As these components, especially sulfur, poison methanol synthesis catalyst irreversibly, Casale provides a guard reactor, contain-ing a hydrolysis
drop very low, so the size, cost and power consumption of the synthesis gas compressor are minimized. catalyst and a zinc oxide bed, either at the suction or at the discharge of the synthesis gas compressor (before the circulator).
Finally, all the reaction heat is recovered in the IMC converter as steam at the correct pressure for direct addition to the natural gas feed. It can work in a temperature range from ambient up to 100°C.

Distillation section
The methanol distillation section is similar to that of the M7000™. Raw methanol synthesis
The three-column arrangement is recommended when energy cost is high whilst, The synthesis loop for the M2000C™ plant is fundamentally the same as for a natural gas-based plant, but with additional pieces
for smaller plants or low energy cost locations, a two-column distillation can be proposed. of equipment and special features of process design such as the guard bed on the make-up gas line, as described above.
Secondly, the gas from coal gasification has a higher reactivity than synthesis gas from natural gas reforming, as the table clearly shows.
This is something of a mixed blessing.

m2000ctm process outline The fact that the make-up gas normally has a low inert content and is rich in carbon makes it possible to achieve high production rates
with low recycle ratios and low catalyst volumes, provided that the converter design is appropriate. The catch is that, as the gas is very
reactive, it can easily cause overheating of the catalyst and hot spots in the converter. That is obviously much less likely to happen
with Casale’s IMC than with a reactor with adiabatic beds.

Synthesis gas generation On account of the low recycle ratio, the loop equipment items are also small in relation to the methanol output, enabling very large
capacities in a single train, much larger than ever achieved so far in any plant of any type, but only if the converter is of the right design.
The process for methanol synthesis from coal gasification is quite different from the natural gas route,
as shown in the block flow diagram below. Distillation section
The methanol distillation section is similar to that of M3000™ or M7000™, and the selection of two or three columns again depends
In coal-based methanol plants the gasifier is third-party technology. Casale is involved as process licensor
on the cost of energy.
in the sections highlighted in red: CO shift, synthesis loop and distillation. Casale also supplies proprietary
equipment for the sour-feed CO shift converters and the IMC methanol synthesis section.

co2 & H2s Syngas Generation Process - Steam Reforming Combined Reforming Coal Gasification

Plant feedstock - NG NG COAL

Specific production MTD/m3cat ~ 15 ~ 20 ~ 30

Converter outlet pressure bar g 80-100 80-100 70-90

coal gasifier co-shift agr synloop CH3OH at converter outlet % mol 4-8 8 - 12 12 - 17

MUG H2/COx mol/mol ~ 3.3 ~ 2.4 ~2

Circulation/MUG mol/mol 4.5-7.5 3.0-4.0 2.5-3.5

o2

methanol 3 columns
asu
distillation

6 7
 casale methanol process M3000tm - M7000tm - M2000ctm

imc - Isothermal methanol converter

synthesis technology

DISTINCTIVE FEATURES The IMC is a quasi-isothermal converter in which the heat transfer
surfaces are plates and the catalyst is loaded outside the cooling pla-

of m3000tm and m7000tm

tes. The Casale IMC design was first applied to methanol synthesis
in 2002, and has achieved important successes in the last ten years.
The following are its main characteristics:
• Perfect control of the temperature profile in the catalyst mass, ena-
bling operation of the converter according to the highest reaction
Pre-reforming reactor technology rate temperature profile.
Casale's pre-reforming reactor utilizes Casale’s extremely well-proven axial-radial flow catalyst bed technology. • The catalyst bed is continuous so it can easily be loaded from the
Casale axial-radial technology has been extensively proved in commercial ammonia and methanol plants, having been used in more than top and unloaded from the bottom through drop-out pipes
500 catalyst beds. • The converter can be designed to incorporate axial-radial flow ca-
talyst bed configuration.
In an axial-radial catalyst bed, most of the gas passes through the catalyst bed in the 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. Thanks to the above features, it is possible to reach the maximum ef-
This layout overcomes the main drawbacks of axial-flow designs, namely the limitation in the maximum capacity that can be reached in ficiency thus minimizing the size and number of the loop equip-ment
a single converter on account of high pressure drop across the bed. It also addresses the main disadvantage of a urely radial-flow design, items and pipes, and optimizing the energy consumption and size of
which is that the bed has to be overfilled with catalyst into ‘dead’ space at the top of the bed to ensure no short-circuiting over the top of the front end.
the catalyst can take place as the catalyst mass settles in use. There is no tube sheet, therefore there is no constraint on the conver-
The essential advantages of the axial-radial concept are: ter size, and the construction is light, consisting of a normal pressure
vessel containing the catalyst bed and the plates.
• low pressure drop, stable with time and not constrained by the catalyst bed;
• full utilization of installed catalyst volume; The plates are fabricated by an automatic production process com-
• possibility to use small-sized catalyst, more active and more resistant to poisons; prising welding with a computer-controlled laser. With only minimal
• lower operating temperature of the vessel wall when the reaction is exothermic (e.g. shift, methanol and ammonia synthesis); manual input, this results in consistently high quality.
Casale axial radial catalyst bed
• possibility to design slim vessels, with important capital cost savings, especially when high-grade construction materials are required, The advantage of the IMC design is that much higher produc-
and no size limitations. tion rates are possible in a single converter, catalyst handling is
Casale’s axial-radial design ensures a perfect gas distribution on the reacting side, controlled by perforated walls (the inlet and outlet collec- easier, and because of the close temperature control in the catalyst
tors). Since the gas distribution is controlled by the walls and not by the catalyst bed, it is not affected by uneven loading, poor distribution or mass, the operating life of the catalyst charge is prolonged.
deterioration of the catalyst or by catalyst aging. At the same time, the gas pressure drop is low and stable throughout the life of the catalyst. For large methanol plants, the most suitable IMC converter configu-
Another advantage that is specific to pre-reformers is that the small-sized catalyst has higher sulfur-resistance and higher activity: as a ration is the steam-raising axial-radial converter, as shown below in
consequence, the catalyst volume is reduced for the same life, with consequent cost savings. cutaway view. The radially-aligned heat exchanger plates are immer-
sed in the catalyst bed and the gas flows inwards between them,
By converting the higher hydrocarbons contained in the natural gas to methane, the pre-reformer protects the plant against coke formation
in the primary reformer feed preheat coil and catalyst tube inlet. That increases the plant reliability. It also allows the steam / carbon ratio imparting essentially all of its reaction heat to raise 25-35-bar steam.
to be reduced, which not only lowers energy consumption but also increases the attainable pre-heat temperature in the pre-reformed Since there is only a single pass, the pressure drop is very low, at
reformer feed, so reducing the radiant duty and cost of the primary reformer. Additionally, some steam reforming of the feed occurs in the about 1 bar. A pump circulates the water/steam mixture through the
pre-reformer, and that further reduces the load on the primary reformer. cooling plates.
The catalyst temperature is controlled by changing the saturated ste-
atr - Autothermal reformer technology am pressure according to the process requirements – for example, to
compensate for declining catalyst activity.
Casale has its own design of ATR, successfully in operation in several plants. The combustion chamber design of the Casale ATR unit is
conceptually very simple. Oxygen is introduced axially at the top of the cylindrical combustion chamber. The process gas is introduced from Since the converter diameter is only marginally influenced by the cir-
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 culation (for a given capacity and make-up condition), the loop recycle
reduces the flame length because the combustion reaction takes place instantaneously after mixing. The short flame does not impinge on ratio can be adjusted to compensate for the declining activity of the
the catalyst surface, which would destroy its top layer, impairing performance and raising pressure drop. catalyst between start-of-run (SOR) and end-of-run (EOR) and main-
tain the desired rate of production. In an axial converter, on the other
The fluid-dynamic field inside the combustion chamber is de-signed to protect the refractory lining from the high-temperature core of the
hand, the recycle rate is constrained by the vessel size, and produc-
flame, preventing hot spots on the lining surface. The burner is provided with a water-cooling system.
tion may suffer at EOR.
This design, which is in service in methanol and ammonia plants, has the following features:
The IMC is also the converter of choice for the M3000™ process ei-
• high reliability and long durability, with no deterioration after several years of operation; ther in axial or axial radial configuration. Possibilities include using the
• high conversion to synthesis gas, thanks to uniformity of temperature and composition; IMC to raise steam or as a boiler feed water preheater, or as a conver-
• longer lasting performance of the catalyst, thanks to the short flame length avoiding impingement on catalyst surface and consequent ter feed gas heater, or with other heat transfer fluids. A combination of
damage; different fluids is also possible.
• total absence of soot formation, as evidenced by analysis and inspections carried out on ATR catalyst and downstream
equipment; In the axial gas-cooled IMC the plates are disposed radially, but the
• wide flexibility: it has been successfully operated at temperature conditions, composition and flow rates far from design. reacting gas flows downwards through the catalyst. In the example
shown in the diagram, the cooling fluid is the fresh synthesis gas.

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 casale methanol process M3000tm - M7000tm - M2000ctm

layer of the catalyst resulting from carry-over of water droplets,

which is not an uncommon occurrence. So, by delivering a

DISTINctive FEATURES
higher suction pressure to the compressor throughout the life
of the catalyst, the axial-radial sour shift technology achieves a

OF m2000ctm
higher production rate.
In conventional shift converters the pressure drop can build up
with time to such an extent that the catalyst has to be changed
before it has reached the end of its active life. Since the pressu-
The Casale technologies applied in new coal-based methanol plants are the sour re drop in the axial-radial sour converter is virtually unaffected
shift converter and, once again, the IMC synthesis technology. by the catalyst, premature change of the catalyst batch is
avoided. Even in the case of the first sour shift converter, which
is the one operating in the most severe conditions, the catalyst
life can be four years or more.
On account of the low pressure drop, the Casale axial-radial
Axial-radial sour CO shift converter sour shift converter can be designed with a much slimmer
pressure vessel than is needed in an axial-flow design and,
As previously mentioned, in a coal-based methanol plant one or more CO shift stages
consequently, a thinner pressure vessel wall. That results in
are needed to adjust the balance of hydrogen and carbon oxides in the synthesis gas.
a significant capital cost saving, especially for the first shift
The design of the CO shift section and converters has an important impact on the
converter.
efficiency and reliability of a methanol plant.
That is not all. Owing to the high operating temperature, an
Especially for large plants, low pressure drop in the shift section over the entire life
axial sour shift reactor must be designed either with a stainless
of the catalyst is essential to minimize the power consumption of the downstream
steel cartridge, and an annulus for flushing the pressure vessel,
synthesis gas compressor. This is especially important when there are multiple shift
or with a refractory lined vessel. In the Casale axial-radial con-
con-verters arranged in series. Also, the shift converter design must be mechanically
verter, on the other hand, the inward gas flow keeps hot gas at
robust and able to withstand the challenging reaction environment. Once again, the
the center of the converter, away from the vessel wall, so that
axial-radial concept provides all the answers.
only the outlet nozzle is exposed to high temperatures, so the
In Casale’s axial-radial sour CO-shift converter concept, the distribution of the gas Casale sour shift converter is much easier, cheaper and robust
over a wide area by the perforated walls ensures low pressure drop, which increases in construction.
little as the catalyst ages or deteriorates and is also unaffected by caking of the top

Casale axial-radial IMC

Principle of Casale axial-radial IMC converter IMC – Ideal for coal-based plants
Casale IMC cooling plates
In coal-based methanol plants, the amount of carbon mono-
xide and carbon dioxide present in the synthesis gas is very
significant. Normally the concentration of these gases is about
15 vol-% CO and 5 vol-% CO2 at the reactor inlet. At such
concentrations the synthesis reaction is quite intense and an
efficient heat sink is needed to control the temperature, not only
to obtain the best equilibrium conversion but also to prevent
damage to the catalyst.
Casale’s steam-raising IMC design is exactly what is required
in these circumstances. The steam pressure of 25-30 bar is
selected because its corresponding temperature level matches
the operating temperature in the catalyst bed well, and the
steam produced can be usefully utilized in the plant.
Steam production in coal-based methanol synthesis loops with
the IMC usually ranges from 1.1 to 1.3 t/t CH3OH, depending on
the temperature of the boiler feed water.

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 FEDERICO BOLLARINO SRL
Via Giulio Pocobelli, 6 | 6900 Lugano | Switzerland (CH)
tel. +41 91 6419200 | fax +41 91 6419291
www.casale.ch | [email protected]

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