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From syngas to methanol

and dimethylether
Ferruccio Trifiro`
Summer School September 2009
Bologna
Content of the lecture
1) Synthesis of methanol from syngas
2) Synthesis of dimethylether (DME) from
methanol
3) Synthesis of DME directly from syngas
Global production of
methanol
The global production of methanol is about 40 million ton
per year, most of which is produced from natural gas.
Today, the high price of oil and natural gas has spurred
new interest in alternative feedstocks for the production
of methanol.
Various types of biomass have been considered, but on
the shorter term coal appears to be the only viable
alternative raw material for large scale methanol
production.
In fact, methanol has been produced from
coal for many years in specific geographical areas,
notably in China.
From methanol to fuels
1) Methanol to DME (alternative to Diesel)
2) Methanol for fuel cell
3) Methanol for production of MTBE
4) Methanol as fuel (altenatives to
gasoline)
5) Methanol for production of hydrogen
6) Synthesis of gasoline (MTG process)
From methanol to chemicals
Methanol
Acetic Acid
Methyl methacrylate
Methyl amines
Methyl formiate
Di-methylterephthalate
Formaldehyde
chloromethanes
From methanol to to
olefins
The different technologies for the future
SYNGAS
CH
3
OH
DME
OLEFINS
PROPYLENE
MTP
MTO
SDTO
From
Methane
Coal
Municipal wastes
Recycled plastics
Biomass Organic
Synthesis of methanol
CO+2H
2
CH
3
OH H
298k
=-90.6kJmol
-1
Methanol synthesis is the second largest
process after ammonia which use catalysts at
high pressure
The mechanism is believed to be
CO+H
2
O-> CO
2
+H
2
H
298k
=-41.2kJmol
-1
CO
2
+2H
2
->CH
3
OH+H
2
O H
298k
= -49kJmol
-1
Operative conditions for
methanol synthesis
Catalyst : CuO(60-70%)- ZnO(20-30%) Al
2
O
3
(5-
15%)or Cr
2
O
3
(5-15%)
Temp 220
o
C-300
o
C
Pressure 50-100Atm (5-10MPa)
Composition of the feed 59 -74%H
2
27- 15% CO
8% C0
2
3%CH
4
Conversion of CO to methanol per pass is normally
16 40 %.
H
2
: CO ratio of 2.17.
The selectivity is around 99.8 %
Commercial Technologies
Today there are four catalyst suppliers and
six companies complete proprietary
processes for methanol synthesis : ICI,
Lurgi, Topse, Mitsubishi, M.W. Kellogg
and Uhde.
Design figures for converters can be as
high as 2,500-10,000 tonnes for day
A good catalyst in a natural gas-based
plant may over its lifetime of about 4 years
Ways to improve the yield in
methanol
1) The reaction is exothermic and favored at
low temperature, for this reason is
necessary to remove the heat to keep the
reaction temperature as low as possible in
order to increase the conversion
2) To remove methanol during the synthesis in
order to shift the equilibrium to higher CO to
methanol conversion per pass (through the
DME formation)
3) To develop more active catalysts which
operate at lower temperature, increasing the
thermodynamically allowed conversion
Equilibrium CO conversion to
methanol (H
2
/CO=2)
400 450
500
550
600
1
0,5
1
1
50bar
100 bar
adiabatic
I
s
o
t
h
e
r
m
a
l
Conversion
Temperature
CO
K
CO +2H
2
->CH
3
OH
The factors affecting on the production
The factors affecting on the production rate in an industrial
methanol reactor are:
1)the thermodynamic equilibrium limitations
2) The catalyst deactivation.
Two zones could be distinguished in the methanol
synthesis reactor with imprecise transition point.
A)The first zone starts from reactor entrance and
continues to a point that conversion approaches to
equilibrium. In this zone the kinetics controls the
process, so increasing temperature improves the rate of
reaction which leads to more methanol production.
B) In the second zone the process switches to equilibrium
and as the temperature increases the deteriorating
effects of equilibrium conversion emerge and decreases
methanol production
Factors which influence activity
Methanol synthesis gas is characterised by the
stoichiometric ratio (H
2
CO
2
) / (CO + CO
2
), often
referred to as the module M. A module of 2 defines a
stoichiometric synthesis gas for formation of methanol.
A high CO to CO2 ratio will increase the reaction rate
and the achievable per pass conversion. In addition, the
formation of water will decrease, reducing the catalyst
deactivation rate.
High concentration of inerts will lower the partial
pressure of the active reactants. Inerts in the methanol
synthesis are typically methane, argon and nitrogen.
Methanol Megaplant
The capacity of methanol plants is increasing to
reduce investments, taking advantage of the
economy of scale.
The capacity of a world scale plant has
increased from 2500 MTPD a decade ago to
about 5000 MTPD today.
Even larger plants up to 10,000 MTPD or above
are considered to further improve economics
and to provide the feedstock for the Methanol-to-
Olefin (MTO) process.
The main sections of methanol
plant
1) In the first section of the plant natural gas
is converted into synthesis gas.
2) In the second section, the synthesis gas
reacts to produce methanol
3) In the tail-end of the plant methanol is
purified to the desired purityl with eventually
the hydrogen recycle
4) utilities

The role of the syngas


production
In the design of a methanol plant the three
sections may be considered independently, and
the technology may be selected and optimised
separately for each section.
The synthesis gas preparation and compression
typically accounts for about 60% of the
investment, and almost all energy is consumed
in this process section. Therefore, the selection
of reforming technology is of paramount
importance, regardless of the site.
The production of syngas
The preferred technologies are:
1) tubular steam reforming
2) two-step reforming (tubular steam reforming
followed by autothermal or oxygen blown
secondary reforming)
3) Autothermal Reforming (ATR) at low steam to
carbon (S/C) ratio is the preferred technology for
large scale plants by maximising the single line
capacity and minimising the investment.
Methanol Synthesis and
Purification
Raw methanol is a mixture of methanol, a small
amount of water, dissolved gases, and traces of by-
products.
Typical byproducts include DME, higher alcohols,
other oxygenates and minor amounts of acids and
aldehydes
The methanol synthesis catalyst and process are
highly selective. A selectivity of 99.8% is not
uncommon.
The design of the reactor
The methanol synthesis is exothermic and
the maximum conversion is obtained at
low temperature and high pressure.
A challenge in the design of a methanol
synthesis is to remove the heat of reaction
efficiently and economically
Multiple
Adiabatic
Tube cooled
BWR
Quench reactor
Quench reactor
A quench reactor consists of a number of
adiabatic catalyst beds installed in series in one
pressure shell. In practice, up to five catalyst
beds have been used. The reactor feed is split
into several fractions and distributed to the
synthesis reactor between the individual catalyst
beds.
The quench reactor design is today considered
obsolete and not suitable for large capacity
plants
Quench reactor
Conversion CO to methanol
Temperature
Conversion
CO
Adiabatic reactors
.
A synthesis loop with adiabatic reactors
normally comprises a number (2-4) of fixed bed
reactors placed in series with cooling between
the reactors. The cooling may realized be by
preheat of high pressure boiler feed water,
generation of medium pressure steam, and/or by
preheat of feed to the first reactor.
The adiabatic reactor system features good
economy of scale. Mechanical simplicity
contributes to low investment cost. The design
can be scaled up to single-line capacities of
10,000 MTPD or more.
Multiple layers adiabatic
converters
conversion
CO
Equilibrium curve
Maximum reaction rate curve
Temperature
C
O
N
V
E
R
S
I
O
N
BWR REACTOR
The BWR(boilng water reactor) is in principle a shell
and tube heat exchanger with catalyst on the tube side.
Cooling of the reactor is provided by circulating boiling
water on the shell side. By controlling the pressure of the
circulating boiling water the reaction temperature is
controlled and optimised. The steam produced may be
used as process steam, either direct or via a falling film
saturator.
The isothermal nature of the BWR gives a high
conversion compared to the amount of catalyst installed.
However, to ensure a proper reaction rate the reactor will
operate at intermediate temperatures - say between
240C and 260C - and consequently the recycle ratio
may still be significant.
Equilibrium CO conversion to
methanol (H
2
/CO=2)
400 450
500
550
600
1
0,5
1
1
50bar
100 bar
adiabatic
I
s
o
t
h
e
r
m
a
l
Conversion
Temperature
CO
K
CO +2H
2
->CH
3
OH
Several industrial processes
ICI adiabatic single bed reactor: the heat of
reaction is removed by adding cold reagent at
different heights in the bed
Lurgi two multitubular reactor: the heat of
reaction is removed in the first reactor by boiling
water around bed in the second reactor by gas
Haldor Topsoe several adiabatic reactors:
arranged in series intermediate cooler remove
heat of reaction
Air product-Chem system three phase fluidized
bed: reactor an inert hydrocarbon liquid inside
the reactor remove the heat
Casale isothermal reactor: the heat is removed
by plates immersed in the catalysts
Lurgi Mega Methanol plant
Lurgis Mega Methanol process is an
advanced technology for converting
natural gas to methanol at low cost in
large quantities.
It permits the construction of highly
efficient single-train plants of at least
double the capacity of those built to date.
The MegaMethanol Concept
The Lurgi MegaMethanol technology has been
developed for world-scale methanol plants with
capacities greater than one million metric tons per
year. The main process features to achieve these
targets are:
1) Oxygen-blown natural gas reforming, either in
combination with steam reforming, or as pure
autothermal reforming.
2)Two-step methanol synthesis in water- and gas-
cooled reactors operating along the optimum reaction
route.
3) Adjustment of syngas composition by hydrogen
recycle.
Lurgi reactor
Lurgi reactor
Main features
The Lurgi reactor is nearly isothermal and
the heat of reaction is used to generate high
pressure steam which is used to drive the
compressor and as distillation steam
Advantages
Optimum temperature profile
Very high gas synthesis conversion
Large reduction of catalyst volume
Lower gas recycle
High energy efficiency
Lurgi reactor- conversion
versus temperature
The synthesis gas production
The synthesis gas production section accounts for 60 %of the
capital cost of a methanol plant. Thus, optimisation of this
section yields a significant cost benefit.
Conventional steam reforming is economically applied in small
and medium-sized methanol plants, with the maximum
single-train capacity being limited to about 3000 mtpd.
Oxygen-blown natural gas reforming, either in combination
with steam reforming or as pure autothermal reforming, is
today considered to be the best suited technology for large
syngas plants.
The configuration of the reforming process mainly depends on
the feedstock composition which may vary from light
natural gas (nearly 100% methane content) to oil-
associated gases.
Lurgi autothermal conversion
desulphurization
.
Steam reforming
Methanol synthesis
Autothermal reforming
Methanol distillate
Air separation
PURE METHANOL
oxygen
Light Natural gas
Air
Process steam
Autothermal Reforming
Pure autothermal reforming can be applied for syngas
production whenever light natural gas is available as
feedstock to the process.
The desulfurised and optionally pre-reformed feedstock is
reformed with steam to synthesis gas at about 40 bar
and higher using oxygen as reforming agent. The
process generates a carbon-free synthesis gas and
offers great operating flexibility over a wide range to
meet specific requirements.
Reformer outlet temperatures are typically in the range of
9501050 C.
Lurgi combined reforming
desulphurization
.
Pre reforming
Methanol synthesis
Autothermal reforming
Methanol distillate
Hydrogen recovery
Air separation
PURE METHANOL
FUEL GAS
oxygen
Heavy natural gas or oil
Air
Lurgi Combined Reforming
For heavy natural gases and oil-associated gases, the
required stoichiometric number cannot be obtained by pure
autothermal reforming, even if all hydrogen available is
recycled. For these applications, the Lurgi MegaMethanol
concept combines autothermal and steam reforming as the
most economic way to generate synthesis gas for methanol
plants. After desulfurisation, a feed gas branch stream is
decomposed in a steam reformer at high pressure(3540 bar)
and relatively low temperature (700800C).The reformed
gas is then mixed with the remainder of the feed gas and
reformed to syngas at high pressure in the autothermal
reactor. This concept has become known as the Lurgi
Combined Reforming Process.
The dual Lurgi reactors
Based on the Lurgi Methanol Reactor and the highly active
methanol catalyst with its capability to operate at high
space velocities, Lurgi has recently developed a dual reactor
system featuring higher efficiency.
The isothermal reactor is combined in series with a gas-cooled
reactor
The first reactor, the isothermal reactor, accomplishes partial
conversion of the syngas to methanol at higher space
velocities and higher temperatures compared with single
stage synthesis reactors. This results in a significant size
reduction of the water-cooled reactor compared to
conventional processes, while the steam raised is available at
a higher pressure.
.
Lurgi Mega Reactors
Lurgi reactor- conversion
versus temperature
Water cooled reactor
Gas cooled reactor
First reactor for Methanol
Synthesis
The Lurgi Methanol Reactor is basically a vertical
shell and tube heat exchanger with fixed tube
sheets. The catalyst is accommodated in tubes and
rests on a bed of inert material.The water/steam
mixture generated by the heat ofreaction is drawn
off below the upper tube sheet. Steam pressure
control permits exact control of the reaction
temperature.This isothermal reactor achieves very
high yields at low recycle ratios and minimizes the
production of by-products.
Second reactor for methanol
synthesis
The methanol-containing gas leaving the first reactor is
routed to a second downstream reactor without prior
cooling. In this reactor, cold feedgas for the first reactor
is routed through tubes in a countercurrent flow with the
reacting gas.
Thus, the reaction temperature is continuously reduced
over the reaction path in the second reactor, and the
equilibrium driving force for methanol synthesis
maintained over the entire catalyst bed.
As fresh synthesis gas is only fed to the first reactor, no
catalyst poisons reach the second reactor. The poison-
free operation and the low operating temperature result
in a virtually unlimited catalyst service life for the gas-
cooled reactor.
Advantages of the Combined Synthesis
Converters
High syngas conversion efficiency. At the same
conversion efficiency, the recycle ratio is about half of
the ratio in a single-stage, water-cooled reactor.
High energy efficiency. About 0.8 t of 5060 bar steam
per ton of methanol can be generated in the reactor.
In addition, a substantial part of the sensible heat can be
recovered at the gas-cooled reactor outlet.
Low investment cost. The reduction in the catalyst volume
for the water-cooled reactor, the omission of the large
feedgas preheater and savings resulting from other
equipment due to the lower recycle ratio translate into
specific cost savings of about 40% for the synthesis loop.
High single-train capacity. Single-train plants with capacities
of 5000 mt/day and above can be built.
Methanol Distillation
The crude methanol is purified in an energy-saving
3-column distillation unit with the 3-column
arrangement,
the higher boiling componentsare separated in two
pure methanol columns.
The first pure methanol column operates at
elevated pressure and thesecond column at
atmospheric pressure. The overhead vapours of
the pressurised column heat the sump of
theatmospheric column. Thus, about 40% of the
heatingsteam and, in turn, about 40% of the
cooling capacity aresaved. The split of the
refining column into two columns
allows for very high single-train capacities.
Lurgi Plant
ICI Reactor
cold
Quench reactor
Conversion CO to methanol
Temperature
Conversion
CO
ICI process
ICI
TOPSOE
REACTORS
methanol
Conversion versus temperature
Topsoe Methanol Process
Based on the unique methanol catalyst, MK-121, Haldor
Topse has developed a methanol synthesis process.
the heart of the synthesis unit is the methanol reactor, a
tubular reactor with catalyst loaded into several tubes
surrounded by a bath of boiling water. The boiling water
efficiently cools the process while at the same time
steam is produced that can be used outside the
methanol synthesis unit. The design of the reactor
ensures that the methanol synthesis is carried out at an
almost isothermal reaction path at conditions close to the
maximum rate of reaction. This ensures a high
conversion per pass and a low formation of by-products.
Topse's methanol synthesis
catalyst MK-121
. Based on an optimised copper dispersion
MK-121 ensures a better preservation of the initial
high catalyst activity as well as an improved
stability compared to its predecessor, MK-101,
while at the same time attaining a remarkable
selectivity. resulting in low by-product formation
over the entire service life. Since the higher
activity of MK-121 allows operation at lower
temperatures, where conditions for by-product
formation is less favourable, the total
.
Topsoe Catalyst MK121
Topsoe catalyst MK 121
Catalyst Loading
The procedure used for catalyst loading is extremely
important, as the catalyst performance depends heavily on
even flow distribution. Therefore, the catalyst should be
loaded as uniformly as possible to ensure that the catalyst
is utilised efficiently. Besides that, the catalyst should be
packed as densely as possible in order to maximise the
installed catalyst activity.
Topse has developed new loading methods, which increase
loading density of the catalyst and improve the flow
distribution through the catalyst bed(s) in various types of
methanol converter designs.
Furthermore, Topse is continuously studying existing
loading procedures in order to develop new innovative
techniques for installing catalyst.
Fluid bed reactor
from Air products
Air product Chem system
Main features
Demonstration plant in Texas
The catalyst is suspended in inert hydrocarbon liquid
which limits the temperature rise and it adsorbs the heat
liberated
Advantages
a higher single pass conversion can be achieved
reducing the syngas compression costs
increase of life of catalyst
Contains low amount o water 1% (the gas phase 4-20%
of water
It is possible to work with 50% CO entering feedstocks
Casale Reactor
The use of axial-radial flow,e, can solve the
problem, of reducing the pressure drop of a
converter. This design can be obtained easily
with the use of plates as cooling surface area,
The flow of cooling gas inside the plates can
have the same direction of the gas in the
catalyst, that is in a horizontal direction, co-
current or counter-current (see figure)
It is clear that an axial radial design leads to a
much slimmer vessel for the same catalyst
volume, allowing to reach capacities above
7000 MTD in a single vessel converter.
Axial radial plate cooled reactor
Axial radial catalyst bed
Methanol Casale reactors
At present more than 10 million tons per year of methanol
are produced worldwide with Methanol Casale
technologies Methanol Casales synthesis converter
technology allows substantial and cost-effective capacity
increases in conventional methanol plants
Methanol Casale is currently licensing, providing basic
design and supplying critical equipment for a 7,000 t/d
methanol plant
A 7,000 t/d plant can be built based on a single methanol
converter. They are the only contractors able to build
real single train, efficient plants with this capacity
Casale and the revamping of
methanol plant
.
, Methanol Casale has also become a leader in
revamping complete methanol plants and in
designing and constructing new ones. Key
achievements in plant upgrading include
capacity increase, reduced specific consumption
of synthesis gas, and improvement in the quality
of the raw methanol.
They revamped 21 ICI plants
Linde reactor
The Linde isothermal reactor is a fixed bed reactor with
indirect heat exchange suitable for endothermic and
exothermic catalytic reactions. This reactor provides the
benefits of a tube reactor while simultaneously avoiding
the heat tension problems of a straight tube reactor.
Gas/gas, gas/liquid and liquid/liquid reactions can be
carried out. The palpable head of gases and liquids as
well as the latent evaporation heat can be used for
cooling or heating operations.
The heating or cooling tube bundle embedded in the
catalyst transfers the reaction heat in such a way that the
catalyst can work at an optimum temperature. This
results in higher outputs, a longer catalyst lifetime, fewer
by-products as well as efficient recovery of the reaction
heat and lower reaction costs.
Linde reactor
Linde isothermal reactor, cross-section with
catalyst and tube bundle
The development of the Linde reactor was
carried out with a particular view toward
exothermic reaction and steam generation.
The reactor is based on the design of the
specially wound heat exchangers, with which
Linde has been able to collect decades of
experience in its own production facilities. The
Linde isothermal reactor is in operation world-
wide in more than 19 plants, among them eight
methanol plants.
Linde Reactor
Isothermal reactor
Section Linde reactor
Linde reactor
. The main principle is that the cooling coil in the
catalyst bed removes the heat of reaction
allowing the catalyst to operate at it's optimum
temperature. This results in higher performance,
longer catalyst life, reduction of by-products, as
well as in high efficiency reaction heat recovery
and lower cost of the reactor.

Toyo
TOYO REACTOR
Toyo reactor
Applicable to 5,000 - 6,000 t/d class large
scale methanol plant with a single train
design
Low Pressure Drop through Catalyst Bed
and Low Utility Consumption
Mild Operating Conditions for Long
Catalyst Life
Maintenability for catalyst exchange
Toyo
TOYO REACTOR
DME in two steps
DME in one step
From methanol to DME
DME synthesis based on methanol dehydration
process is very simple.
2 CH3OH -> 2DME + H
2
O
The dehydration of methanol is a gas phase and
exothermic reaction, the heat of reaction
(approx.23 kj/mol) is considerably small
compared with methanol synthesis reaction.
The selectivity of DME in methanol
dehydration is very high and is approx. 99.9 %.
Dehydration catalyst is of gamma alumina
basis
Operative conditions for DME
Feed methanol is fed to a DME reactor
after vaporization.
The synthesis pressure is 1.0 - 2.0 MPa.
The inlet temperature is 220 - 250 C and
the outlet is 300 - 350 C.
Methanol one pass conversion to DME is
70 85 % in the reactor.
DME Plant
1) Produced DME with by-product water and
unconverted methanol is fed to a DME column
after heat recovery and cooling.
2) In the DME column DME is separated from
the top as a product. Water and methanol are
discharged from the bottom and fed to a
methanol column for methanol recovery.
3) The purified methanol from the column is
recycled to the DME reactor after mixing with
feedstock methanol. The methanol consumption
for DME production is approximately 1.4 ton-
methanol per ton-DME.
DME PLANT
DME
REACTOR
C
H
3
O
H
D
M
E
DME
TANK
RAW METHANOL
FUEL GAS
WATER
D
M
E
C
o
l
u
m
n
DME COLUMN
METHANOL
COLUMN
DME from syn- gas
. The synthesis of DME from synthesis gas involves three
reactions:
1) CO
2
+3 H
2
->CH
3
OH+H
2
O
2)CO+H
2
O-> CO
2
+H
2
3) 2 CH
3
OH ->2CH
3
OCH
3
+H
2
O
The introduction of Reaction (3), the DME synthesis, serves
to relieve the equilibrium constraints inherent to the
methanol synthesis by transforming the methanol into DME.
Moreover, the water formed in Reaction (3) is to some
extent driving Reaction (2) to produce more hydrogen, which
in turn will drive Reaction (1) to produce more methanol.
Thus, the combination of these reactions results in a strong
synergetic effect, which dramatically increases the synthesis
gas conversion potential.
From syngas to DME
The catalyst applied is a proprietary dual-function
catalyst, catalyzing both steps (i.e., methanol and
DME synthesis) in the sequential reaction.
Significant advantages arise by permitting the
methanol synthesis, the watergas shift, and the
DME synthesis reaction to take place
simultaneously. This methanol synthesis is
restricted by equilibrium, which requires high
pressure in order to reach an acceptable
conversion
A dual catalyst system is based on a combination
[of Cu/ZnO/Al
2
O
3
catalyst and gamma-alumina
(this issue) catalyst.:
Dalian Institute of Chemical
Physics
In the mid-1990s, DICP was awarded two
patents in the United States concerned
with the conversion of methanol/dimethyl
ether (DME) to light olefins. These
patents are the basis for the syngas via
dimethyl ether to olefin process (SDTO).
Catalyst foDME from syngas
Bifunctional metal (Cu, Zn, etc.)-zeolite
catalysts have been developed, which can
convert syngas very selectively to DME
with high carbon monoxide (CO)
conversion (this reaction is far more
favorable thermodynamically than
methanol synthesis from syngas).
.
).
Advantages of SDTO
Syngas to DME breaks the thermodynamic limit
of syngas to methanol system with up to over 90
percent CO conversion, 5-8 percent investment
savings and 5 percent operational cost savings.
Syngas to DME breaks the thermodynamic limit
of syngas to methanol system with up to over 90
percent CO conversion, 5-8 percent investment
savings and 5 percent operational cost savings.
Storage and Handling of methanol
.
Methanol is stable under normal storage conditions. but
can react violently with strong oxidizing agents.
The greatest hazard involved in handling methanol is
the danger of fire or explosion.. Methanol is aggressive
toward copper, zinc, magnesium, tin, lead, and
aluminum, which should therefore be avoided. Similarly,
the use of plastics for storage is not recommendedBoth
floating- and fixed-roof tanks are used for large-scale
methanol storage.
Blanketing the tank vapor space in combination with a
closed vent recovery system may be required by local
environmental regulations.