Advances in methanol synthesis

F
or many years, methanol has been used
primarily as a chemical intermediate in
manufacturing plastics and resins, then
more recently in the manufacture of methyl terti-
ary butyl ether (MTBE) for use as a lead
anti-knock replacement and octane enhancer,
allowing a methanol derivative to enter the
transportation fuel chain in a signifcant way for
the frst time. However, now methanol is being
seen as a product that can be introduced directly
into the gasoline pool by blending, allowing
indigenous resources to be used and providing a
diversity of supply that can help to reduce
dependence on crude oil and attempt to break
the cycle of apparently ever-escalating oil prices.
China has introduced a national M85 standard
that sees gasoline blended with 85% methanol,
which has been manufactured using Chinas cheap
and abundant supplies of coal, helping to reduce
its dependence on expensive imported oil.
In the US, there is considerable support for the
Open Fuel Standard Act, which, if passed, would
call for car manufacturers to introduce fexible
fuel vehicles that can run on methanol/ethanol/
gasoline mixtures. Currently, there is little meth-
anol production left in North America, but the
development of shale gas is set to reduce natural
gas prices signifcantly in North America. And,
like China, the US has abundant coal reserves,
which, through methanol, could be used to
displace oil imported from abroad.
In this article, we will look at methanol synthe-
sis catalysts and discuss the various changes that
have occurred in the Katalco range of catalysts
against the backdrop of changing industry
requirements.
Methanol production
ICI initiated work on catalysts for methanol
Terry Fitzpatrick and Tom Hicks Johnson Matthey Catalysts
synthesis in the 1920s, when the only commer-
cial process operated at high pressure. Following
early research on copper-zinc catalysts, ICI
announced the Low Pressure Methanol (LPM)
process in 1963 and the frst single-train produc-
tion unit started operation in 1966.
JM Catalysts has recently developed a new
generation of copper zinc methanol synthesis
catalysts called Katalco Apico. This extends the
performance of the Katalco 51 series catalysts
an improvement that is a step change in
methanol synthesis catalysis.
Methanol synthesis catalysts
Since the initial development of the frst copper-
zinc low-pressure methanol synthesis catalyst,
Katalco 51-1, continuing development program-
mes have improved performance in terms of
activity, by-products production, strength,
shrinkage and overall life. The original catalyst
was designed for application in the multi-bed ICI
Quench lozenge converter, and an early variant,
Katalco 51-2, quickly became the industry stand-
ard. As additional technologies were developed,
different types of converter were used, the most
noteworthy being gas-cooled and steam-raising
in both axial and radial fow confgurations.
www.digitalrening.com/article/1000297 Catalysis 2010 1
Catalysts with higher and more stable activity enable cost savings and boost
output in methanol production
JM
Competitor
A
B r
o t i t
e
p
m
o
C
Others
Figure 1 Methanol technology market shares
These often impose different requirements on
the catalyst, so JM Catalysts has developed a
range of synthesis catalysts.
It is worth considering the various changes
that have occurred in Katalco catalysts against
the backdrop of changing industry requirements.
These changes do not come from any one aspect
of the catalyst. The enhancements have been
generated by identifying and understanding the
role of the key components in the formulation
and the catalyst manufacturing process itself, as
well as improvements in manufacturing control.
Catalyst activity
The methanol synthesis reaction is an example
of a structure insensitive catalytic reaction one
2 Catalysis 2010 www.digitalrening.com/article/1000297
in which the activity is wholly
dependent on the total exposed
copper area and not affected by
the structure of the crystallites.
Figure 2 illustrates this direct
relationship between activity
and copper surface area for
catalyst operating under indus-
trial conditions.
This relationship led to
suggestions that maximum
activity would be achieved with
the highest CuO content in the
fresh formulation, but this
ignored the impact of formula-
tion. As Figure 3 shows,
variations in the CuO:Al
2
O
3

ratio have a marked effect on
the relative activity, as shown in accelerated life
tests.
High initial activity, while important, is not
paramount, as the effective useful life of the
catalyst will be governed by its stability with
time, so the formulation must also stabilise the
copper surface area under the process conditions
to which it is exposed. Thermal sintering is a key
mechanism for synthesis catalyst deactivation
with operation at temperatures as high as 315C,
depending on reactor type. Commonly found
poisons such as sulphur and, in some cases, iron
and nickel carbonyls brought into the loop with
fresh syngas also contribute to deactivation or
die off. Thus, key formulation requirements are
stabilisation of the copper surface area and self-
guarding against poisons.
One of the major contribu-
tors to a signifcantly increased
in-service activity was the
incorporation of magnesia
(MgO) into the formulation
during the early 1990s. This
gave rise to Katalco 51-7 and
has been incorporated in
subsequent variants Katalco
51-8 and Katalco 51-9. The
beneft from incorporating
MgO is evident from Figure 4,
and the signifcant improve-
ment relative to Katalco 51-2 in
terms of both initial and fnal
activities is illustrated in
Figure 5.
Cu metal area, m
2
/g
2
4
6
8
l0
l2
0
0 l0 30 40 50 20
S

l
o
m

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l
-
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l
-
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l

X

6
CuO/SiO
2
CuO/MnO
CuO/MgO
CuO/ZnO/Al
2
O
3
Figure 2 Variation in synthesis catalyst activity with copper surface area
Figure 3 The impact of catalyst formulation on catalyst activity
CuO, %
Activity
Optimum ratio
Al
2
O
3
l.20
l.25
l.30
l.35
l.40
l.45
l.l5
y
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a

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P
l
A
2
O
3
%

,
2 Catalysis 2010 www.digitalrening.com/article/1000297
Activity testing is a special-
ised technique comparing aged
activities to the catalyst Katalco
51-2. Ageing is reliably simu-
lated by deactivation in a
controlled and reproducible
manner using elevated temper-
atures and pressure plus a
representative synthesis gas
mixture, before measuring
activity under standard condi-
tions. A typical test regime
measures the activity after 144
hours on-line, representing
approximately three months in
an operating methanol plant.
The results have been validated
over the years using data from
operating charges in plants and
side-stream reactors on our own
plants.
Activities are regularly
compared with the leading
competitive offerings, and the
most recent comparison in
Figure 6 clearly shows the rela-
tive benefcial performance of
Katalco 51-9S. The higher and,
more critically, stable activity
allows operation at lower
temperatures, favouring the
reaction thermodynamics and
loop carbon effciency, mini-
mising thermal sintering and
giving benefts in increased
methanol output and reduced
by-product formation. The
reduced rate of activity loss
translates into a longer period
of operation between catalyst
changes.
Catalyst strength and
shrinkage
Declining strength and activity
were originally the limiting
factors of the catalysts opera-
tional life. Due to the high
copper content, initial catalyst
reduction and development of
the copper surface area leads
to major changes in the
www.digitalrening.com/article/1000297 Catalysis 2010 3
MgO, %
42
44
46
48
54
52
50
56
40
0.0 l.5 l.5 2.5 2.0 3.0 l.0
m

,
a
e
r
a

e
c
a
f
r
u
s

r
e
p
p
o
C
2
g
/
Figure 4 Effect of incorporating magnesia on copper surface area
Katalco 5l-2 Katalco 5l-9S
y
t
i
v
i
t
c
a

e
v
i
t
a
l
e
P
Calculated initial activity, v/v
Calculated final activity, v/v
Figure 5 Katalco 51 series activity enhancement
Katalco 5l-9S Competitor
y
t
i
v
i
t
c
a

e
v
i
t
a
l
e
P
Calculated initial activity, v/v
Calculated final activity, v/v
Figure 6 Comparison of commercial catalyst activities
physical structure, which is manifested in terms
of shrinkage and reduced strength. Low strength
during operation, especially during upset condi-
tions, can lead to physical breakage of the
pellets, giving increased pressure drop that
reduces effciency as well as affecting gas distri-
bution through the catalyst. High shrinkage also
leads to distribution problems and a reduced
volume of active copper in the reactor. These
properties are critical, for instance, in a steam-
raising reactor such as the axial fow
catalyst-in-tube design, where the catalyst duty
is quite arduous both in terms of the volume of
material charged and the crushing forces to
which the catalyst is exposed during thermal
cycling.
Initially, in the oxidised state, the catalyst must
be strong enough to withstand the rigours of
charging into the chosen reactor design without
breakage. Too high an initial as received
strength derived from a high pellet density can
be a disadvantage, leading to diffusional limita-
tions within the catalyst, affecting overall activity.
Through an understanding of the formulation
and manufacturing parameters, Katalco 51-9S
has been designed with a high pellet density,
giving a much enhanced strength both initially
and in operation without adding any diffusion
limitations, as shown in Berty reactor tests and
commercial experience.
The most readily obtainable measure of
strength is the mean horizontal crush strength
(MHCS), appropriately measured across the
weakest pellet dimension. Occasionally, the
mean vertical crush strength (MVCS) is
reported, but this can be misleading, being an
order of magnitude higher in the as received
state.
As a result of improvements to the catalyst
formulation and manufacturing process, pres-
sure drop increase is no longer a limiting feature
of normal plant operation. In particular, the
introduction of post-pellet treatment to the
manufacturing process in 2001 has resulted in
catalysts that have much greater reduced
strength and as little as 5% shrinkage on
reduction.
Catalyst lives of four to six years, and occa-
sionally as long as eight years, are commonplace,
even in the arduous catalyst-in-tube steam-
raising duty discussed in the case study
below.
Choice of catalysts
JM Catalysts currently offers four methanol
synthesis catalysts; namely, Katalco 51-8, Katalco
51-8PPT and Katalco 51-9S and the premium
product Katalco Apico. Providing a range of cata-
lysts, and not relying on a single universal
product, caters for the different methanol
synthesis technologies and enables a choice of
product for the specifc duty. This is particularly
pertinent in a climate where feedstocks are
changing. Natural gas has been the principal
feed for synthesis gas generation (accounting for
~80% of world methanol production); synthesis
gas generation historically has largely been based
on pure steam methane reforming, whereas
more recently there are circumstances when
combined reforming, which includes an oxygen-
fred secondary or ATR, has its merits.
Coal gasifcation is another method of syngas
generation seeing rapid expansion in the
number of medium- and large-scale methanol
projects in China based on a relatively cheap
and plentiful resource, with many more plants
likely to appear in the future. The US, Australia,
India and Russia also have abundant supplies
of coal. In relation to the actual converter type,
and without going in to too much detail, the
different syngas-generating technologies yield
different syngas compositions (for instance, CO
content), each composition yielding different
reaction rates over the synthesis catalyst.
Consideration of the exothermic synthesis reac-
tions means that some converter designs are
better suited than others to the different synthe-
sis gases, by virtue of their reaction heat
removal systems. These include, but are not
limited to, the direct quench-cooled adiabatic
converter design, the axial steam-raising cata-
lyst-in-tube design or the catalyst-in-shell-side,
gas-cooled design such as the tube-cooled
converter. Furthermore, the savings through
economies of scale that might be accrued from
building world-scale methanol plants can bene-
ft from the use of radial fow converters such
as the Davy Process Technology radial steam-
raising converter.
Case study: Titan Methanol
This Lurgi-designed plant has a nameplate
capacity of 2500 tpd and the synthesis loop
comprises two parallel steam-raising converters,
each charged with 60m
3
of Katalco 51-9S.
4 Catalysis 2010 www.digitalrening.com/article/1000297
Experience has shown that
with this type of
reactor careful initial catalyst
charging is essential to ensure
minimum pressure drop vari-
ation between tubes, to give
an even fow distribution and
maximum use of the relatively
small volume of catalyst. The
catalyst has been producing
record production levels of
2600 tpd since May 2005,
giving signifcant fnancial
beneft.
As a result of the enhanced
performance of the catalyst,
an extended run of four years
is planned. JM Catalysts has
provided detailed technical
support throughout, carrying
out frequent performance
optimisations. Figure 7
confrms the activity achieved,
which is 20% greater than
Katalco 51-8 at end of life.
Figure 8 shows the pressure
drop has remained stable with
time, confrming the high
strength retention and resist-
ance to breakage in this duty.
Benets
Since ICI frst developed the
LPM process, copper-based
catalysts have improved in
small incremental steps at
regular intervals until now.
The immediate benefts to
methanol plant operators are signifcant:

Increased production

Lower by-product formation

Faster start-ups using pre-reduced catalyst

Fewer catalyst change-outs.

Simply stated, in existing plants, Katalco Apico
will make the most methanol, give the longest
life and the fastest start-up possible. For a newly
designed plant, it offers the smallest reactor and
the highest achievable effciency. The following
sections show comparative data for Katalco
Apico and the current industry standard Katalco
51-9S.
Highest and most stable catalyst activity
Comparative activity tests and projections clearly
show the higher activity of Katalco Apico catalyst
(see Figure 10).
As a direct result of the higher activity and
stability with time on-line, the catalyst can be
operated for twice as long as any comparable
commercial catalyst, leading to fewer catalyst
change-outs. On a 2500 tpd plant currently
achieving four years between change-outs, the
typical time saved by doubling the catalyst life is
about nine-and-a-half days, equivalent to at least
23 750 tonnes of product methanol. This is
derived from savings on oxidation of the
www.digitalrening.com/article/1000297 Catalysis 2010 5 4 Catalysis 2010 www.digitalrening.com/article/1000297
Time on-line, months
0.2
0.4
0.6
0.8
l.0
0.0
0.0 6.0 l2.0 30.0 24.0 36.0 42.0 48.0 l8.0
y
t
i
v
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t
c
A
Katalco 5l-9S activity
Katalco 5l-8 predicted activity
Figure 7 Activity of Katalco 51-9S
Time on-line, months
0.750
l.000
l.250
l.500
0.500
0.0 5.0.0 l0 l5.0 20.0 25.0 30.0 35.0 40.0
r
a
b

,
p
o
r
d

e
r
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s
s
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r
p

d
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a
e
M
Figure 8 Pressure drop stability of Katalco 51-9S with time
previous catalyst charge prior to
discharge, time to discharge and
refll and then reduce the new
catalyst charge.
By-product formation
The results of tests shown in Figure
11 confrm an even lower level of
higher alcohol and other oxygenate
by-products with Katalco Apico at
typical operating conditions. The
beneft is further enhanced by being
able to operate the catalyst at the
lowest temperature possible due to
stable activity.
On a 2500 tpd unit, using the
current generation of catalysts,
98.5% of the crude methanol
coming from the synthesis loop is
converted to product methanol.
With a 50% reduction in higher
alcohol by-products, this fgure is
increased to 99.15% an increase
of 0.65% in methanol produced.
Greater strength
Figure 12 shows the measured in-
situ radial pellet strength compared
with the best currently available
product.
The 50% increase in operating
strength ensures the catalyst is
better able to withstand upset
conditions without physical break-
age. This results in a more stable
pressure drop so that effciency and
gas distribution are maintained.

Pre-reduced catalyst
Katalco Apico catalysts are
supplied in the reduced form, which
ensures the catalyst has been acti-
vated to achieve maximum unit
activity. Since there is no shrinkage
associated with normal catalyst
reduction, this also maximises the
amount of active copper charged. By
using a pre-reduced catalyst, there is
a typical saving of around 30 hours
for a new charge, representing at
least 3000 tonnes of product metha-
nol on a 2500 tpd plant.
6 Catalysis 2010 www.digitalrening.com/article/1000297
L
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Long
e
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M
o
st methanol productio
n
M
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-
u
p
Pre-reduced
catalyst
Highest
activity
Strongest
product
available
slowest
deactivation
Least
by-products
Apico
Figure 9 Sources of benets to operators
Lquivalent years on-line
0
0 l 2
Katalco Apico
Katalco 51-9S
3 4
y
t
i
v
i
t
c
A
Figure 10 Enhanced activity of Katalco Apico
Feature Benet to operator Extra MeOH, tonnes
Pre-reduced catalyst Faster start-up 3000
Higher, stable activity Additional MeOH made 55 000
Doubled catalyst life Eliminated change-out 23 750
50% lower by-products Increased efciency 45 000
Total 126 750
Operating benets of Katalco Apico
Table 1
6 Catalysis 2010 www.digitalrening.com/article/1000297
Overall benet
As indicated in the previous
sections, the enhanced
performance of Katalco
Apico leads to benefts in
many aspects of plant opera-
tion. These are summarised
in Table 1.
The total value of these
benefts is over $25 million
in additional methanol sales
(assumed methanol price
$200/t). Additional savings
related to manning and
material costs of shutdown
may also be realised.
Case study: Katalco
performance
A methanol plant in Asia
using a combination of
Katalco catalysts in the tubu-
lar reformer contracted JM
Catalysts to do a specialist
reformer survey to check the
performance and make
recommendations for any
possible optimisation. The
furnace was found to be in
need of balancing and it was
also shown that the process
gas temperature could be
safely increased without
compromising tube life.
Detailed recommendations
on balancing the furnace
were implemented on the
plant, with a resultant
increase of 60 tpd of metha-
nol make worth over $3
million/y.
KATALCO
JM
and APICO
JM
are marks of the Johnson Matthey Group
of Companies.
Terry Fitzpatrick is Methanol Technology Manager within the GTL
group of Johnson Matthey Catalysts. His work has a particular
emphasis on the development of technology and catalyst
applications for methanol chemistry. He joined the catalyst
business (then ICI) over 20 years ago and has a bachelors degree
in chemical engineering from Cambridge University, UK.
Tom Hicks is a consultant with Johnson Matthey Catalysts. He
has worked on steam reforming catalysts and technology, shift
and methanol catalysts, acetylene hydrogenation catalysts and
ammonia synthesis technology for ICI and now Johnson Matthey,
and has a degree in chemistry from Durham University, UK.
www.digitalrening.com/article/1000297 Catalysis 2010 7
2
4
6
8
l0
l2
0
Katalco Apico
h
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n
|
Katalco 5l-9S
Figure 12 In-situ radial pellet strength of Katalco Apico
50
l00
l50
200
250
300
0
Katalco 5l -9S Katalco Apico
m
p
p

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Lthanol
2-Propanol
l-Propanol
MLK
2-8utanol
2-Methyl propan-l-ol
l-8utanol
Figure 11 Selectivity improvement with Katalco Apico

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