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Methanol
Application: To produce methanol from natural gas. The process is based
on Casale highly efficient equipment including: The Casale plate cooled
technology for the methanol converter.
9
7
1
Economics: Thanks to the high efficiency of the process and equipment design, the total energy consumptions (evaluated as feeds + fuel
+ steam import from package boiler and steam export to urea) is about
7 Gcal/metric ton of produced methanol.
4
3
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Methanol
Application: To produce methanol from natural gas. The process is based
on Casales highly efficient equipment, including its:
Casaleaxial-radialpre-reformer
Casalehigheficiencydesignfortheauto-thermal
reformer (ATR)
Casaleplate-cooledtechnologyforthemethanolconverter.
19
8
7
1
14
4
3
18
12
11
5
13
10
6
17
15
16
recoveryunit(HRU)(16)andrecycledtothesynthesisloop.Theremaininginerts(17)aresenttotheprimaryreformer(4)asafuel.
The raw methanol (14) is sent to the distillation section (18), comprising three columns, where byproduct and contained water are separated out to obtain the desired product purity (19).
Commercial plants:FourATRplantsareinoperation,one7,000metric
tpdplantisunderconstruction,andsevenplate-cooledconvertersare
in operation.
Licensor:MethanolCasaleSA,Switzerland-CONTACT
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Methanol
Application: The Davy Process TechnologyJohnson Matthey process is
a low-pressure methanol process. The process produces methanol from
natural or associated gas via a reforming step or from syngas generated
by the gasification of coal, coke or biomass. The reforming step, also
available from this licensor, may be conventional steam reforming (SMR),
compact reforming, autothermal reforming (ATR), combined reforming
(SMR + ATR) or gas-heated reforming (GHR + ATR). The reforming or
gasification step is followed by compression, methanol synthesis and
distillation (one, two or three column designs) Capacities up to 7,000
metric tpd, are practical in a single stream and flowsheet options exist
for installation of the process offshore on FPSO vessels.
HP steam
Methanol product
BFW
6
Distillation
Natural
gas
4
2
BFW
Steam
Water from
distillation
8
9
10
CO2 (optional)
7
Fuel to
reformer
Crude
methanol
Continued
Methanol, continued
Economics: Outside of China, recent trends have been to build methanol plants in regions offering lower cost gas (such as North Africa, Trinidad and the Arabian Gulf). In these regions, total economics favor low
investment rather than low-energy consumption. Recent plants have an
energy efficiency of 7.2 Gcal/ton7.8 Gcal/ton. Choice of both synthesis
gas generation and synthesis technologies is on a case-by-case basis. In
China, the trend has been for coal-gasification based methanol production to be built. However, where gas based production has been built,
the higher gas costs favor higher energy efficiency.
Offshore opportunities globally continue to create interest in order
to access low-cost gas reserves, facilitate oil/condensate extraction and
avoid flaring.
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Methanol
Fired
heater
Description: Natural gas is preheated and desulfurized. After desulfurization, the gas is saturated with a mixture of preheated process water
from the distillation section and process condensate in the saturator.
The gas is further preheated and mixed with steam as required for
the pre-reforming process. In the pre-reformer, the gas is converted to
H2, CO2 and CH4. Final preheating of the gas is achieved in the fired
heater. In the autothermal reformer, the gas is reformed with steam
and O2. The product gas contains H2, CO, CO2 and a small amount of
unconverted CH4 and inerts together with under composed steam. The
reformed gas leaving the autothermal reformer represents a considerable amount of heat, which is recovered as HP steam for preheating
energy and energy for providing heat for the reboilers in the distillation section.
The reformed gas is mixed with hydrogen from the pressure swing
adsorption (PSA) unit to adjust the synthesis gas composition. Synthesis
gas is pressurized to 5 10 MPa by a single-casing synthesis gas
compressor and is mixed with recycle gas from the synthesis loop. This
gas mixture is preheated in the trim heater in the gas-cooled methanol
reactor. In the Lurgi water-cooled methanol reactor, the catalyst is fixed
in vertical tubes surrounded by boiling water. The reaction occurs under
almost isothermal condition, which ensures a high conversion and
eliminates the danger of catalyst damage from excessive temperature.
Exact reaction temperature control is done by pressure control of the
steam drum generating HP steam.
The preconverted gas is routed to the shell side of the gascooled methanol reactor, which is filled with catalyst. The final
conversion to methanol is achieved at reduced temperatures along
Saturator
Desulfurization
Oxygen
Process
condensate
Fuel
Natural
gas
Distillation
reboiler
Water
cooled
reactor
Pure
methanol
Prereformer
Auto thermal
reformer
HP steam to
oxygen plant
LP steam
Gas
cooled
reactor
BFW
Distillation
Pressure
swing
adsorption
H2
the optimum reaction route. The reactor outlet gas is cooled to about
40C to separate methanol and water from the gases by preheating
BFW and recycle gas. Condensed raw methanol is separated from the
unreacted gas and routed to the distillation unit. The major portion
of the gas is recycled back to the synthesis reactors to achieve a high
overall conversion. The excellent performance of the Lurgi combined
converter (LCC) methanol synthesis reduces the recycle ratio to about
2. A small portion of the recycle gas is withdrawn as purge gas to
lessen inerts accumulation in the loop.
In the energy-saving three-column distillation section, low-boiling
and high-boiling byproducts are removed. Pure methanol is routed to
the tank farm, and the process water is preheated in the fired heater
and used as makeup water for the saturator.
Continued
Methanol, continued
Economics: Energy consumption (natural gas) for a stand-alone plant,
including utilities and oxygen plant, is about 30 GJ/metric ton of methanol. Total installed cost for a 5,000-mtpd plant including utilities and
oxygen plant is about US$350 million, depending on location.
Commercial plants: Forty-nine methanol plants have been licensed applying Lurgis Low-Pressure methanol technology. Six MegaMethanol
licenses are in operation; two are under construction and a MegaMethanol license has been awarded with capacities up to 6,750 metric tpd
of methanol.
Licensor: Lurgi GmbH, a member of the Air Liquide Group - CONTACT
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Methanol
Application: To produce federal-grade AA refined methanol from natu-
O2
7
ral gas-based synthesis gas and naphtha using Toyo Engineering Corp.s
(TOYOs) Synthesis Gas Generation technologies and proprietary MRF-Z
reactor. In a natural gas-based plant, the synthesis gas is produced by reforming natural gas with steam and/or oxygen using high-activity steam
reforming ISOP catalyst.
Description:
BFW
8
9
1
6
CW
10
Crude methanol
Natural gas,
naphtha
Steam
BFW
Heat
rec.
4
11
12
Methanol
BFW
Fusel oil
Process water
Commercial plants: TOYO has accumulated experience with 20 methanol plant projects.
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Methanol
Process Categories
Feedstock
Company Index
Feed
Fuel
Desulfurization
Saturator
Reformer
Description: The methanol plant consists of the process steps: feed purification, steam reforming, syngas compression, methanol synthesis and
crude methanol distillation. The feed is desulfurized and mixed with
process steam before entering the steam reformer. This steam reformer
is a top-fired box type furnace with a cold outlet header system developed by Uhde. The reforming reaction occurs over a nickel catalyst.
Outlet-reformed gas is a mixture of H2, CO, CO2 and residual methane.
It is cooled from approximately 880C to ambient temperature. Most of
the heat from the synthesis gas is recovered by steam generation, BFW
preheating, heating of crude methanol distillation and demineralized
water preheating.
Also, heat from the flue gas is recovered by feed/feed-steam
preheating, steam generation and superheating as well as combustion
air preheating. After final cooling, the synthesis gas is compressed to
the synthesis pressure, which ranges from 30 100 bara (depending on
plant capacity) before entering the synthesis loop.
The synthesis loop consists of a recycle compressor, feed/effluent
exchanger, methanol reactor, final cooler and crude methanol separator.
Uhdes methanol reactor is an isothermal tubular reactor with a copper
catalyst contained in vertical tubes and boiling water on the shell side.
The heat of methanol reaction is removed by partial evaporation of
the boiler feedwater, thus generating 11.4 metric tons of MP steam
Circulator
MUG compression
3 column
distillation
BFW
Condenser
Methanol
reactor
Product
Separator
Intermediate
storage tank
per metric ton of methanol. Advantages of this reactor type are low
byproduct formation due to almost isothermal reaction conditions,
high level heat of reaction recovery, and easy temperature control by
regulating steam pressure. To avoid inert buildup in the loop, a purge is
withdrawn from the recycle gas and is used as fuel for the reformer.
Crude methanol that is condensed downstream of the methanol
reactor is separated from unreacted gas in the separator and routed
via an expansion drum to the crude methanol distillation. Water and
small amount of byproducts formed in the synthesis and contained in
the crude methanol are removed by an energy-saving three-column
distillation system.
Continued
Copyright 2010 Gulf Publishing Company. All rights reserved.
Methanol, continued
Economics: Typical consumption figures (feed + fuel) range from 7 to
8 Gcal per metric ton of methanol and will depend on the individual
plant concept.
Commercial plants: Eleven plants have been built and revamped worldwide using Uhdes methanol technology.
Licensor: Uhde GmbH is a licensee of Johnson Matthey Catalysts LowPressure Methanol (LPM) Process - CONTACT
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Steam
Saturator
Oxygen
Prereformer
1
2
Hydro- Sulfur
genator removal
Steam
Methanol
reactor
Secondary
reformer
Steam
4
Steam
reformer
Natural gas
Makeup
compressor
3
5
7
Condensate
Light ends to fuel
Raw
methanol
Product methanol
Water
9
Raw
methanol
storage
the methanol plant. Total energy consumption for this process scheme
is about 7.0 Gcal/ton including energy for oxygen production.
Company
Product
Feedstock
Process description
No. of
licenses
Date
of last
license
Ethylene Oxide
48
2009
Ethylene oxide
Ethylene
Process produces ethylene oxide (EO) from the direct oxidation of ethylene using the Dow
METEOR process
18
NA
Ethylene oxide
Direct oxidation process using high-selectivity catalyst with high product yields
NA
NA
78
2010
2009
Glycol Ethers
1974
Methanol
The process produces methanol from natural gas or associated gas via a reforming step or
from syngas generated by gasification of coal, coke or biomass. The reforming/gasification
step is followed by compression, methanol synthesis and distillation
87
2010
Methanol Casale SA
Methanol
Natural gas
To produce methanol from natural gas. The process is based on Casale's highly efficient
plate-cooled technology for the methanol converter
NA
NA
Methanol Casale SA
Methanol
Natural gas
To produce methanol from natural gas. The process is based on Casale's highly efficient
axial-radial pre-reformer, high-efficiency auto-thermal reformer design and plate-cooled
technology for the methanol converter
12
2010
Methanol
Federal-grade AA refined methanol is produced from natural gas-based synthesis gas and
naphtha using Synthesis Gas Generation technologies and proprietary MRF-Z reactor.
20
NA
Lurgi GmbH
Methanol
Oxygen-operated syngas generation, two-step isothermal synthesis with maximum yield and
very large single-train capacity
40
2000
Uhde GmbH
Methanol
11
NA
Methanoltwo-step
reforming
Process produces methanol from natural or associated gas feedstocks using two-step
reforming followed by low-pressure synthesis.
NA
NA
Axens
CATACOL technology ensures high MTBE yields by combining catalysis and distillation
separation
26
2009
Saipem S.p.A./Ecofuel
S.p.A.
Multipurpose plant. High efficiency, flexibility and reliability. Compact and low-investment
plants
23
2006
CDTECH
Mixed ethers
MTBE, TAME and heavier ether production from hydrocarbon feeds containing C4, C5, C6 and
C7 iso-olefins
2000
CDTECH
MTBE
Mixed C4 hydrocarbons
High-conversion catalytic distillation process for MTBE using C4s and methanol
107
2000
Natural detergent
alcohols
Fatty acids
Natural detergent alcohols are produced from fatty acids using esterification, hydrogenolysis
and refining
NA
Cumene
Oxidization of cumene with air at high efficiency (+95%) produces cumene hydroperoxide
(CHP) which is concentrated and cleaved under high-yield conditions (+99%) to phenol and
acetone in the presence of an acid catalyst
25
NA
Lummus Technology
Cumene
Cumene oxidation process with ability to produce alphamethylstyrene and pharmaceuticalgrade acetone byproducts
2008
I-9
Phenol