Ammonia catalyst developments

Indo-Topsøe Club, Ammonia meeting

Sybille Zola Mortensen, Sales Manager, smzm@topsoe.dk
Agenda
¡ Hydrogenation
¡ Reforming
¡ Low temperature shift
¡ Ammonia synthesis
Market share ammonia plants, India
Linde 3%
Haldor Topsøe 79%
KBR 18%
 Market share ammonia plant catalysts, India

Other 11%
Haldor Topsøe 45%

Süd-Chemie 38%
Johnson Matthey 6%
Hydrogenation
catalyst
 Topsøe syngas hydrogenation catalysts
Catalyst TK-261 TK-261
NiO, wt % 2.3
MoO3, wt% 10
Shape Quadralobe
Size, mm 2.5

¡ New generation ¡ Less stacking of the active sites

¡ Less clustering of the active sites
hydrogenation catalyst ¡ Higher catalyst activity

¡ Enhanced metal dispersion

¡ Superior activity
Stacking Clustering
¡ No CO2 sensitivity
Benefits of TK-261
Example:
¡ 5 ppm organic sulfur
¡ Catalyst lifetime: 5 years
¡ TK-250 design volume: 16.8 m 3

Option 1: Short loading

Only 14.3 m3 TK-261 required
Catalyst volume reduced by 15%

Option 2: Increased lifetime

16.8 m3 TK-261 installed
Lifetime increased to 6.5 years
DFT simulation of hydrogenation at BRIM™ site

Hydrogen
Carbon
Molybdenum
Nickel
Sulphur

STM image of NiMoS cluster

Journal of catalysis, vol. 248, 2007 and vol. 268, 2009
C4H4S + 3H2 ↔ H2S + C4H8
Reforming catalyst
Reforming catalyst
¡ Optimizing active phase
– Activity
– Poison capacity
¡ Carrier material
– Thermal stability
– Resistance to carbon
formation
¡ Alkali promotion
¡ Catalyst shape
R67 series of conventional reforming catalysts and
– Pressure drop RK series of alkali promoted reforming catalysts
– Mechanical strength
– Surface area
– Heat transfer
Nickel content and reforming activity

Relative reforming activity

Ni content
Sintering of metal particles
¡ Particle migration and
coalescence
¡ In-situ recording
¡ Atom migration
Active sites
¡ Two types of active sites
Terrace
¡ Terrace and step sites site
Ni(111),
¡ Step sites far most active 0.20nm
¡ Fine Ni crystal dispersion Ni(200),
give higher Ni surface area 0.18nm

¡ More step sites and higher

activity Step
site

1mbar H2 at 500°C
Nature 427, 426 (2004)
Poison capacity
¡ Step sites
Terrace
poisoned first site
¡ High catalyst
Step
activity give high site
poison capacity

Nisurface + H2S ↔ S-Nisurface + H2

Carrier material and carbon formation

Higher Alkaline
Ca-Mg-aluminate
Haldor Topsøe
carrier
Mg-alumina spinel
Carbon resistance

Acidity

Ca-aluminate

Alumina
Lower Acidic
 Optimizing catalyst shape
¡ Pressure drop
¡ Particle size
¡ Heat transfer
¡ Particle shape
¡ Flow properties
¡ Number and size of ¡ Surface area
holes
¡ Mechanical strength

Topsøe 7H catalyst
The optimal combination
Reforming catalyst carrier Topsøe 7H

¡ 1520 MTPD ammonia plant

¡ R-67-7H installed from 1996 to 2012
¡ Average plant load of 120%
Competitor

15 Methane leakage, %

10

Topsøe 7H in a melted reformer tube

5
Pressure drop, Bar

0
0 20 40 60 80 100 120 140 160 180
Months on stream
Low temperature
shift catalyst
Topsøe low temperature shift catalysts
¡ Reducing methanol
formation
– Saving H2

LSK-2 – Environmental issues

¡ Optimizing sintering
LK-821-2
barriers
LK-823 – Stabilizing the high initial
LK-853 FENCE™ activity
¡ FENCE™ technology
Reducing methanol formation
¡ CO2 + 3H2 ↔ CH3OH + H2O
¡ Promoters for reducing methanol formation
¡ The challenge of balancing promoter content
¡ Proprietary promoter combination developed

Methanol formation
Shift conversion

Promoter content
Optimizing sintering barriers
¡ Copper crystals finely dispersed for high activity
¡ Sintering barriers introduced
¡ Stabilization of nano-sized copper particles achieved

Optimized energy barrier for sintering

Cu crystal Cu
Energy

ZnO
Al2O3

Cu crystal
FENCE™ technology
¡ Cu crystals separated by
a fence of metal oxides
¡ FENCE™ technology in
LK-853 FENCE™
– Unmatched stability
– Superior activity
– Outstanding poison
resistance
 Advantages with LK-853 FENCE™

0.4

0.3
CO, %

0.2
LK-823
0.1
LK-853 FENCE™

0
0 10 20 30 40 50 60 70 80 90 100
Time, months
LK-853 FENCE™ - industrial experience
¡ First references installed in October 2011
¡ Currently operating in 13 plants
¡ Performance data confirms all
expectations for LK-853 FENCE™
MeOH concentration, ppm wt
REAL DATA: methanol by-product formation

600

LK-823
400 LK-853 FENCEä

200

0
0 200 400 600 800 1000
Days in service
REAL DATA: Superior activity

LK-853 FENCEä
Cu

FENCEä technology
Relative activity

Al2O3 LK-823
ZnO

0 6 12 18 24 30 36
Catalyst age (months)
Ammonia synthesis
catalyst
Topsøe ammonia synthesis catalyst
KM1

¡ High and very stabile activity

¡ Track record of very long lifetimes
– 85 current references have operated KM1 for more than 10 years
– 44 current references have operated KM1 for more than 15 years
– 17 current references have operated KM1 for more than 20 years
¡ Prereduced version for significantly faster start-up
¡ Excellent poisoning resistance
Stability
¡ Structural promoters Fe

– Al2O3
– CaO
– MgO
– SiO2
¡ Enhances thermal
stability
Catalyst activity Good promotion
¡ Inhibits sintering of
Fe crystals
Poor promotion

Time on stream
Worldwide success of KM1
¡ More than 240 KM1 references around the world

¡ 60% of ammonia production worldwide is produced using KM1

¡ Topsøe has supplied more than 1,000 charges of KM1 catalyst
Thank you for your attention