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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
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.