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 manufac-
ture of methyl tertiary 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 gaso-
line 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 fex-
ible fuel vehicles that can
run on methanol/ethanol/gasoline
mixtures. Currently, there is little
methanol 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
Catalysts with higher and more stable activity enable cost savings and boost
output in methanol production
Terry FiTzpaTriCk and Tom HiCks
Johnson Matthey Catalysts
methanol synthesis 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 synthesis in the 1920s,
when the only commercial process
operated at high pressure. Follow-
ing early research on copper-zinc
catalysts, ICI announced the Low
Pressure Methanol (LPM) process
in 1963 and the frst single-train
production unit started operation in
1966.
JM Catalysts has recently devel-
oped 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
programmes have improved
performance in terms of activity,
by-products production, strength,
shrinkage and overall life. The orig-
inal catalyst was designed for
application in the multi-bed ICI
Quench lozenge converter, and an
early variant, Katalco 51-2, quickly
became the industry standard. As
additional technologies were devel-
oped, different types of converter
were used, the most noteworthy
being gas-cooled and steam-raising
in both axial and radial fow confg-
urations. These often impose
different requirements on the cata-
lyst, so JM Catalysts has developed
a range of synthesis catalysts.
It is worth considering the vari-
ous changes that have occurred in
Katalco catalysts against the back-
drop of changing industry
requirements. These changes do not
come from any one aspect of the
catalyst. The enhancements have
www.eptq.com CATALYSIS 2010 47
JM
Competitor
A
B r
o t i t
e
p
m
o
C
Others
Figure 1 Methanol technology market shares
Now methanol is
being seen as a
product that can be
introduced directly
into the gasoline pool
by blending
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 contributors to
a signifcantly increased in-service
activity was the incorporation of
magnesia (MgO) into the formula-
tion 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 improvement rela-
tive to Katalco 51-2 in terms of both
initial and fnal activities is illus-
trated in Figure 5.
Activity testing is a specialised
technique comparing aged activities
to the catalyst Katalco 51-2. Ageing
is reliably simulated by deactiva-
tion in a controlled and reproducible
manner using elevated tempera-
tures and pressure plus a
representative synthesis gas
mixture, before measuring activity
under standard conditions. A typi-
cal test regime measures the activity
after 144 hours on-line, represent-
ing 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 offer-
ings, and the most recent
comparison in Figure 6 clearly
shows the relative benefcial
performance of Katalco 51-9S. The
higher and, more critically, stable
activity allows operation at lower
temperatures, favouring the reac-
tion thermodynamics and loop
carbon effciency, minimising ther-
mal sintering and giving benefts in
increased methanol output and
reduced by-product formation. The
reduced rate of activity loss trans-
lates into a longer period of
operation between catalyst changes.
Catalyst strength and shrinkage
Declining strength and activity
were originally the limiting factors
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 insensi-
tive catalytic reaction one 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
industrial conditions.
This relationship led to sugges-
tions that maximum activity would
be achieved with the highest CuO
content in the fresh formulation,
but this ignored the impact of
formulation. As Figure 3 shows,
variations in the CuO:Al
2
O
3
ratio
have a marked effect on the
relative activity, as shown in accel-
erated life tests.
High initial activity, while impor-
tant, 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
48 CATALYSIS 2010 www.eptq.com
Cu metal area, m
2
/g
2
4
6
8
l0
l2
0
0 l0 30 40 50 20
S

l
o
m

,
y
t
i
v
i
t
c
a

s
i
s
e
h
t
n
y
s

l
o
n
a
n
t
e
M
l
-
g

l
-
0
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
t
i
v
i
t
c
a

e
v
i
t
a
l
e
P
l
A
2
O
3
%

,
of the catalysts operational life.
Due to the high copper content,
initial catalyst reduction and devel-
opment of the copper surface area
leads to major changes in the physi-
cal structure, which is manifested
in terms of shrinkage and reduced
strength. Low strength during oper-
ation, especially during upset
conditions, can lead to physical
breakage of the pellets, giving
increased pressure drop that
reduces effciency as well as affect-
ing gas distribution 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 cata-
lyst 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 with-
out breakage. Too high an initial
as received strength derived from
a high pellet density can be a disad-
vantage, leading to diffusional
limitations within the catalyst,
affecting overall activity. Through
an understanding of the formula-
tion 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. Occasion-
ally, 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 manu-
facturing process, pressure drop
increase is no longer a limiting
feature of normal plant operation.
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
/
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
Figure 4 Effect of incorporating magnesia on copper surface area
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
50 CATALYSIS 2010 www.eptq.com
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
u
s
s
e
r
p

d
e
r
u
s
a
e
M
Figure 8 Pressure drop stability of Katalco 51-9S with time
reaction heat removal systems.
These include, but are not limited
to, the direct quench-cooled adia-
batic converter design, the axial
steam-raising catalyst-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 build-
ing world-scale methanol plants can
beneft 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. Experience has shown that
with this type of reactor careful
initial catalyst charging is essential
to ensure minimum pressure drop
variation between tubes, to give an
even fow distribution and maxi-
mum 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 through-
out, carrying out frequent
performance optimisations. Figure
7 confrms the activity achieved,
which is 20% greater than Katalco
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
i
t
c
A
Katalco 5l-9S activity
Katalco 5l-8 predicted activity
Figure 7 Activity of Katalco 51-9S
www.eptq.com CATALYSIS 2010 51
In particular, the introduction of
post-pellet treatment to the manu-
facturing 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 occasionally 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 catalysts, 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 particu-
larly pertinent in a climate where
feedstocks are changing. Natural
gas has been the principal feed for
synthesis gas generation (account-
ing for ~80% of world methanol
production); synthesis gas genera-
tion 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 rela-
tively 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 compo-
sition yielding different reaction
rates over the synthesis catalyst.
Consideration of the exothermic
synthesis reactions means that some
converter designs are better suited
than others to the different
synthesis gases, by virtue of their
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.
Benefts
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 compara-
tive 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 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
activated to achieve maximum unit
activity. Since there is no shrinkage
associated with normal catalyst
reduction, this also maximises the
L
o
w
e
s
t

r
a
t
e

o
f

p
r
e
s
s
u
r
e
d
r
o
p
in
crease
Longe
st liv
e
s
a
n
d
f
e
w
e
s
t

c
a
t
a
l
y
s
t

c
h
a
n
g
e
s

M
o
st methanol productio
n
M
o
r
e

m
e
t
h
a
n
o
l

a
n
d

i
m
p
r
o
v
e
d

e
f
f
i
c
i
e
n
c
y
P
a
s
t
e
s
t

s
t
a
r
t
-
u
p
Pre-reduced
catalyst
Highest
activity
Strongest
product
available
slowest
deactivation
Least
by-products
Apico
Figure 9 Sources of benefts to operators
52 CATALYSIS 2010 www.eptq.com
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
2
4
6
8
l0
l2
0
Katalco Apico
h
t
g
n
e
r
t
s

h
s
u
r
c

l
a
i
d
a
r

u
t
i
s

n
|
Katalco 5l-9S
Figure 12 In-situ radial pellet strength of Katalco Apico
Feature Beneft 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 effciency 45 000
Total 126 750
operating benefts of katalco apico
Table 1
amount of active copper charged.
By using a pre-reduced catalyst,
there is a typical saving of around
30 hours for a new charge, repre-
senting at least 3000 tonnes of
product methanol on a 2500 tpd
plant.
overall beneft
As indicated in the previous
sections, the enhanced performance
of Katalco Apico leads to benefts in
many aspects of plant operation.
These are summarised in Table 1.
The total value of these benefts is
over $25 million in additional meth-
anol 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 tubular 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 balanc-
ing and it was also shown that
the process gas temperature could
be safely increased without compro-
mising tube life. Detailed
recommendations on balancing the
furnace were implemented on the
plant, with a resultant increase of
60 tpd of methanol 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
bachelors degree in chemistry from Durham
University, UK.
www.eptq.com CATALYSIS 2010 53
50
l00
l50
200
250
300
0
Katalco 5l -9S Katalco Apico
m
p
p

,
l
o
n
a
h
t
e
m

e
d
u
r
c

n
i

n
o
i
t
a
r
t
n
e
c
n
o
C
Lthanol
2-Propanol
l-Propanol
MLK
2-8utanol
2-Methyl propan-l-ol
l-8utanol
Figure 11 Selectivity improvement with Katalco Apico