AmoMax-10 – A novel Ammonia

Synthesis Catalyst
Ammonia synthesis catalysts have been based on iron since the first commercial production in 1913. Conventional
ammonia synthesis catalysts are made of magnetite (Fe3O4) with structural and electronic promoters. However, Süd-
Chemie now is manufacturing an ammonia synthesis catalyst based on non-stoichiometric iron oxide, wustite (Fe1-xO)
with a cubic crystal structure. This catalyst is more active at lower temperature and lower pressure and hence, allows a
more efficient ammonia production.

Norbert Ringer; Dr. Marcus Michel

Süd-Chemie AG, Munich, Germany

Rob Stockwell
Süd-Chemie Inc., Louisville, KY, USA

Summary are made of magnetite (Fe3O4) with a number of struc-

tural and electronic promoters.

T his paper summarizes the features of a com-

pletely new generation of ammonia synthe-
sis catalyst. The catalyst is still iron based,
however, the iron oxide is of so-called wustite crystal
structure. Results from extensive laboratory tests and
However, Süd-Chemie now is manufacturing an
ammonia synthesis catalyst on the basis of a non-
stiochiometric ferrous oxide, so-called wustite (Fe1-xO).
Wustite has a cubic crystal structure compared to
the spinel-like structure of magnetite. This allows to
from first charges in ammonia plants on commercial provide a catalyst with an improved pore structure,
scale are discussed within the paper and confirm the higher surface area and better mechanical strength.
higher activity of this catalyst. This novel ammonia The designation of the novel catalyst is AmoMax-
synthesis catalyst allows a more efficient ammonia pro- 10. The catalyst is supplied in its oxidic form and is
duction and new ammonia plant flowsheets with also available as pre-reduced and stabilized in air.
smaller synthesis converter catalyst volume or lower
temperatures and loop pressures. This high performance Reaction
catalyst provides a very significant contribution to an
improved ammonia plant efficiency and economy. Ammonia is an inorganic chemical, but is produced
using organic feedstocks such as natural gas, naphtha,
coal and oil residues. Most of the production of ammo-
Introduction nia worldwide is based on steam reforming of natural
gas. Hydrogen from this synthesis gas reacts under high
Ammonia synthesis catalysts have been based on
pressure with nitrogen from air and forms ammonia in
iron oxide since their first commercial production in the
an exothermic equilibrium reaction.
early 1910s. Conventional ammonia synthesis catalysts

AMMONIA TECHNICAL MANUAL 232 2005

 A schematic flow diagram is shown in Fig. 1.
S te a m A ir

H C F e ed

H TS

P u rif ic a tion P re R e fo rm e r P rim ar y Re f or m e r S e con d a ry R e fo rm er

C O2

R ef orm in g

A m m on ia

H T CO S h if t L T C O Sh ift C O 2 Re m o v a l M e t ha n a tio n N H 3 Syn th e sis Lo o p

The process for producing ammonia on an indus- ing through cold synthesis gas (quench converter;
trial scale was developed by Fritz Haber and Karl Fig. 2) or by indirect cooling (heat exchange; Fig. 3 –
Bosch and is since then referred to as the 4) via cold synthesis gas or steam raising.
Haber/Bosch process. The first industrial ammonia The pseudo isothermal tube cooled converter with
plant commenced it production in 1913 at BASF in cooling tubes inside the catalyst bed or with catalyst in-
Ludwigshafen. side the tubes and the coolant on the shell side plays
only a minor role in the ammonia industry.
N2 + 3 H2 ÅÆ 2 NH3 + Heat
The following reactor drawings represent ammonia
The thermodynamic equilibrium of this reaction converter designs widely used in the industry. Figure 2
is favored by: shows a four bed axial flow converter with quench gas
cooling (i.e. Kellogg Brown & Root).
• Low temperature The second one (Fig. 3) represents a two bed radial
• High pressure flow converter (Haldor Topsoe).
Last but not least (Fig. 4), a three bed axial-radial
However, catalyst reaction rates (kinetics) are in- flow reactor (Casale design) is shown.
creased by higher temperature and pressure.

As a result, most of the ammonia synthesis loops

utilize converters with multiple beds and inter bed
cooling. Current industrial ammonia processes differ
primarily in reactor design. Commercial converters
divide catalyst into individual beds where reaction
takes place adiabatically. Between the individual
catalyst beds the heat of reaction is removed by cool

2005 233 AMMONIA TECHNICAL MANUAL

 Fig. 2: Axial flow, quench gas converter Fig. 4: Three bed axial-radial flow
OUTLET MAIN INLET
QUENCH GAS QUENCH QUENCH

HEAT
EXCHANGER

CATALYST
CATALYST BEDS
BEDS

HEAT
EXCHANGER
CATALYST
BASKET
CATALYST
BASKET PRESSURE
VESSEL
PRESSURE
VESSEL
HEAT
EXCHANGER

MAIN INLET COLD

BYPASS OUTLET
Typical reaction temperatures ranges from 350 –
500°C (660 – 930°F) and loop pressure from 100 – 300
bar (1450 – 4350 psi).
Novel Catalyst
Catalysts are of no doubt absolutely crucial to the
performance of the process stage in which they are
Fig. 3: Two bed radial flow
used. Since the design of ammonia plants have become
QUENCH GAS tighter, high performance and reliable catalysts became
of more and more importance. A higher catalytic activ-
MAININLET ity at lower pressure plays a major role for smaller and
cheaper reactor designs and a more efficient ammonia
production.
This growing importance led to the development of
a novel ammonia synthesis catalyst. For almost a cen-
CATALYST tury, ammonia synthesis catalysts have been based on
BEDS
iron. Conventional ammonia synthesis catalysts are
made by fusing natural magnetite (Fe3O4) with potas-
sium carbonate, alumina and other components, such as
CaO, SiO2 and other metal oxides.
CATALYST The melt is cast onto a rotating plate and solidified.
BASKET
The solidified material is crushed into small fragments,
PRESSURE which afterwards are screened into classes of different
VESSEL
particle sizes (i.e.: 1.5 – 3 mm or 6 – 10 mm).
Now Süd-Chemie is manufacturing a novel ammo-
HEAT
EXCHANGER
nia synthesis catalyst, AmoMax-10, which is based on a
ferrous oxide, so called wustite. Wustite is a non-
stoichiometric iron oxide (Fe1-xO) with a cubic crystal
OUTLET structure. Where x is ranging from 0.03 – 0.15.

AMMONIA TECHNICAL MANUAL 234 2005

 The picture below exhibits the natural form of the Fig. 6: Catalyst Activity
mineral wustite.
Amomax-10 R (752°F)
Fig. 5: Mineral wustite
Amomax-10 400°C
Magnetite 425°C
(797°F)
0 5 10 15 20 25
Am m onia Conc. [vol%]

Figure 6 proves the higher activity of both Amo-

Max-10 and AmoMax-10 R (pre-reduced and stabi-
lized) in comparison to the magnetite reference catalyst.
Activity is expressed as the concentration of ammonia
in the exit gas from the lab scale reactor. The kinetic
evaluation of the above tests yields a 70 % higher activ-
ity by applying the commonly used kinetic model.
Figure 7 shows the formation of ammonia by scan-
ning a temperature range of 350 – 500°C (660 – 930°F).
Structural and electronic promoters of AmoMax-10 Thermodynamic equilibrium of the formation of am-
catalyst Ca, Al, K and rare earth elements. monia is also shown for the same temperature range.

The non-stoichiometric ferrous oxide allows to de- Fig. 7: AmoMax-10 and Magnetite vs. Temperature
sign a catalyst with an improved pore structure and 24
Equilibrium
higher specific surface area for much higher catalytic 22

activity at lower temperature and pressure. Because of a 20

Ammonia [vol%]

deficit in oxygen in the crystal structure, AmoMax-10 18

is easier and faster to activate. Of equal importance is
16
its higher mechanical strength for the retention of low Amomax-10
Magnetite
pressure drop over the entire useful life of this catalyst. 14

AmoMax-10 catalyst is also available pre-reduced 12

and stabilized in air. 10

340 360 380 400 420 440 460 480 500 520
Temperature [°C]

Laboratory Tests AmoMax-10 catalyst has a significantly better ac-

tivity at lower temperature compared to magnetite. This
Activity test comparing AmoMax-10 with
is very favorable since the equilibrium in the lower
Magnetite
temperature range would be very high.
A number of tests on lab scale were conducted in
parallel tubular micro reactors with sized catalyst parti- Figure 8 shows that AmoMax-10 also has a sub-
cles of 0.35 – 0.84 mm. A space velocity of 15 000 stantially better performance than the magnetite refer-
Nm³/m³/h is used and a pressure of 150 bar (2177 psi) is ence at the lower end. This test was conducted in a
applied. For those tests, a commercially available mag- pressure range of 8 – 22 Mpa (80 – 220 bar; 1160 –
netite catalyst was used as a reference. 3190 psi), other conditions being equal to the other
tests.
Both, the low temperature activity and the high ac-
tivity at low pressure, allow the design of new ammonia
flowsheets.

2005 235 AMMONIA TECHNICAL MANUAL

 Fig. 8: AmoMax-10 and Magnetite vs. Pressure The catalyst is made of irregular shaped granules
with rounded ends (additional process step). This al-
30
lows even and dense packing of the catalysts in the
25 converter, which is important for an uniform flow dis-
tribution and high performance.
Ammonia Conc. [vol%]

20

15
Amomax-10
Catalyst bed bulk density is:
Manetite
10

• 3.0 – 3.3 kg/l (oxide form)

5
• 2.4 – 2.6 kg/l (pre-reduced form)
0
5 7 9 11 13 15 17 19 21 23
Pressure [Mpa] AmoMax-10 catalyst is available in all the common
granule sizes (i.e., 1.5 – 3 mm, 6 – 10 mm, 8 – 12 mm).
Other advantages are the high crushing strength (all
dense loaded methods can be utilized for catalyst load-
In addition to the above performance tests, a cata- ing) and resistance to the usual catalyst poisons (oxy-
lyst life test was conducted to prove the extreme gen containing compounds such as water and carbon
thermo-stability and longevity of AmoMax-10 catalyst. oxides are temporary poisons like for a magnetite cata-
Figure 9 shows the result of a life test which was con- lyst).
ducted for 2000 hours in laboratory at a temperature of
425°C (797°F), pressure of 150 bar (2177 psi) and
space velocity of 15000 Nm³/m³/h. A temperature of References
425°C was chosen to stay away from thermodynamic
(equilibrium) controlled region. vAmoMax-10 catalyst has been supplied to four
ammonia plants in China, among those to Liaohe
Fig. 9: Life Test Chemical Fertilizer, Shuangtaizi, Liaoning province
(Kellogg 1000 MTPD, KRES front-end), to one plant in
Russia (Perm Azot, 1400 MTPD), to another plant AMI
30 Agrolinz, Linz, Austria (500 MTPD, Uhde). Operating
25
data from those reference plants prove the better per-
formance of AmoMax-10 catalyst versus conventional
20 magnetite catalyst. The following Table 1 indicates the
Ammonia [vol%]

current users and technology.

15

10 Table 1: Users List

5

0
0 500 1000 1500 2000
Hours on Stream

Catalyst Features
As already mentioned above, AmoMax-10 catalyst
is available in the oxide form as well as in the pre-
reduced form. Typically, the pre-reduced catalyst is
loaded in the first bed. The slightly higher active cata-
lyst of the oxide form is used to the best advantage in
the lower beds, where both the temperature and the
chemical potential of the reaction are lower.

AMMONIA TECHNICAL MANUAL 236 2005

 Experience New plants could be designed for lower pressure
operation and with a smaller synthesis converter.
This all together leads to lower capital expenditure
AmoMax-10 catalyst is in operation at the reference and lower energy costs.
plant of Liaohe in China. The plant was revamped by The activation of this catalyst is fast and easy which
Kellogg Brown & Root by installing the KRES unit. 78 saves time and cost.
m³ of this catalyst was installed about two years ago. AmoMax-10 clearly is a perfect low cost alternative
Since then, AmoMax-10 catalyst is performing as per to Ru/C catalyst.
our expectations. Figure 10 compares its activity with
the previously used magnetite catalyst.

Fig. 10: Perfomance at Liaohe Chemical Group,

PRC

10
9
8
7
Catalyst Activity

6
5
4
3
2
1
0
-1 1 3 5 7 9 11 13 15
Years on Stream

Amomax-10 Magnetite

Life time of AmoMax-10 is expected to be at least

the same 10 – 15 years as per any magnetite catalyst.

In addition to the above reference, 45 m³ of this

new catalysts was loaded into the axial-radial synthesis
converter (Casale revamp) at Perm Azot, Russia. The
catalyst even exceed the expectations there. The loop
performs at lower pressure and delivers 1420 MTPD
compared to the design capacity of 1370 MTPD.

Conclusion
A novel ammonia synthesis catalyst has been de-
veloped (AmoMax-10). The new catalyst is still iron-
based, however, uses a different iron oxide source,
wustite. Compared to the classic magnetite based am-
monia synthesis catalyst, AmoMax-10 exhibits an about
70 % higher catalytic activity.
The higher activity allows lower operating tempera-
tures and loop pressures. Existing loops can utilize this
by running at minimum possible loop pressure for ex-
tended period of time. This allows to improve ammonia
plant performance, efficiency and economy without the
need of any revamping.

2005 237 AMMONIA TECHNICAL MANUAL