Ammonia synthesis catalysts in action

John Brightling
25 Mar 2015
Westin Hotel Gurgaon, India

Agenda
Introduction and history
Catalyst Chemistry
Proven references in action
KATALCOJM 35-4
KATALCOJM 74-1

Worlds largest plants

Performance in Dual Pressure Process

BASF patent for ammonia production

(1908)

Fritz Haber

Patent Certificate
3

First continuous ammonia production

(1909)

Catalyst development

Alwin Mittasch
Max Appl, The Haber-Bosch Process and the Development of Chemical Engineering from: A Century of
Chemical Engineering, Edited by Wiliam F. Furter, Plenum Publishing Corporation, 1982.

Reactor development

Carl Bosch

Max Appl, IFA Technical Conference, September 25.-26., 1997, Sevilla,Spain

6

Reactor development

BASF Information,
8/1974

Centrifugal machines

General trends
140

First
BASF
UHDE
3300tpd
expertise
becomes
start-up
acquired
partner

3000

Plant Capacity

2500

120

100

2000

80

1500

60

1000

40

500

20

0
1930

1940

1950

1960

1970

1980

1990

2000

Energy Consumption

3500

0
2010

Year of Commissioning

Johnson Matthey ammonia synthesis

Long history in ammonia
synthesis
ICI heritage (ICI 35 Series)
BASF heritage (S6-10)
KATALCOJM 35 Series

High activity KATALCOJM 74-1

series catalyst
AMV process
LCA Process
Dual Pressure Process

Chemistry of Ammonia Synthesis

Ammonia chemistry

Exothermic reaction
Conversion favored by high pressure and low temperature
Rate of reaction increases as pressure increases
Temperature is a balance of kinetics and equilibrium
No by-products

N2 + 3 H2

2 NH3
H(700K) = - 52kJ/mol

Formulation
Magnetite (Fe3O4) precursor
Controlled reduction
Pre-reduction or in situ
reduction
Oxygen is removed from the
crystal lattice without shrinkage
Produces extremely porous
metallic iron structure
Key to achieving a high activity
catalyst

Promoters boost catalyst

performance

Effect of Promoters and Stabilisers

Promoter

Effect

AI2O3

Stabilises the internal surface

MgO

Increases the thermal stability

SiO2

stabilises activity in presence of

oxygen compounds during normal
operation and reduction.

K2O

increases intrinsic activity of Fe

particles

CaO

protects the K promoter against

neutralisation and increases the
stability against poisoning by sulphur

CoO

increases intrinsic activity

Need to balance activity, reduction

speed and lifetime

KATALCOJM Ammonia Synthesis

Proven catalyst references in action

Proven performance - catalysts

= KATALCOJM 35-series
~36

= KATALCOJM S6-10
(equivalent to 35 series)
~19
= KATALCOJM 74-series
~8

Proven performance - converters

= Uhde ~24

= ICI ~3

= Kellogg/KBR ~9

= Casale ~20

= Topsoe ~1

= Other ~5

KATALCOJM 35 Series

Ammonia Synthesis

Images courtesy of BASF

1913 converter

2015 ammonia converter

using KATALCOJM 35-8 magnetite

Magnetite based catalysts

Generically called conventional magnetite
BUT magnetite catalysts are NOT all the same!

Accelerated laboratory tests;

High GHSV => not close to equilibrium;
Shows intrinsic activity differences.

References in India
Customer A in India
Capacity 1890 MTPD
14 m3 KATALCOJM 35-8A and 58m3 KATALCOJM 35-4A
Commissioned in April 2013

Customer B in India
Capacity 1350 MTPD
16m3 KATALCOJM 35-8A and 67m3 KATALCOJM 35-4A
Commissioned in June 2013

Case Study Revamped Kellogg converter

Customer A, India
Capacity
: 1890 MTPD
Commissioned : April 2013
KBR converter revamped by
Casale
3 bed with cold shots and
interchangers
Casale slotted plate collector
Wet MUG changed to dry
Loaded pre-reduced catalyst in
Bed 1 and unreduced catalysts
in Bed 2 & 3

Case Study Revamped Kellogg converter

1890 MTPD Plant , India

Operating around 105% of plant rated capacity
Conversion achieved per pass: 16-17% of NH3
Production details:
Year

Age
(year)

Make
(MTPD)

Inlet
pressure
(kg/cm2)

May 2013

1965

178

Apr 2014

1956

170

Nov 2014

1.6

1943

169

Conversion per pass better/comparable to a similar converter

with a leading competitors product

Case Study Casale converter

Casale Converter - 3 beds with i/cs - 1350 MTPD, India
Commissioned in June 2013
Parameter

Units

Measured

Fitted

Optimized

barg

130

130

130

Converter inlet temperature

179

182

185

Converter exit temperature

433

433

441

Converter exit NH3

%(mol)

17.4

17.6

18

Ammonia make

te/day

1410

1410

1438

Converter inlet pressure

Operating around 105% of rated capacity

Catalyst reduction
Reduction of catalyst was completed as expected
First bed pre-reduced catalyst reduced with once through
system & other beds through circulation system
Performance of the catalyst is in line with expectation

Case Study 1 KBR converter Asia

1350mtpd Kellogg - 2 bed inter-cooled horizontal beds

Case Study 1 KBR converter Asia

Higher NH3 Conversion

Lower NH3 loop pressure

Case Study 1 KBR converter Asia

Case Study 2 Casale converter UK

Plant design 1150 mtpd, 3-bed Casale converter
KATALCOJM 35-8A catalyst installed 2006
Record production achieved
Make
(mtpd)

Inlet
Pressure
(barg/psig)

Catalyst
Age
(years)

Aug 2006

1474

208 / 3020

Jun 2008

1504

211 / 3060

Jul 2012

1634

209 / 3030

Jul 2013

1578

201 / 2910

Case Study 3 Uhde converter MENA

Capacity: 1200 mtpd

Commissioned 1998
One Ammonia reactor
with 3 radial beds

Case Study 3 Uhde converter MENA

Commissioned Oct 1998
Name plate production with loop pressure 11barg (165psi)
below design at 15 years
KATALCOJM 35-4 capable of much higher production if
more syngas is available
Make
(mtpd)

Inlet
Pressure
(barg/psig)

Catalyst
Age
(years)

Design

1200

190 / 2760

Sep 2012

1206

181 / 2625

14

Mar 2013

1206

179 / 2595

15

Case Study 4 Uhde converter MENA

Capacity: 2000 mtpd

Commissioned 2004

Two Ammonia reactors

1st & 2nd radial bed, HP Boiler,
3rd radial bed

Case Study 4 Uhde converter MENA

2000mtpd plant
Commissioned 2004
Has achieved 20% above nameplate without being on a
synthesis catalyst limit
Make
(mtpd)

Inlet
Pressure
(barg/psig)

Catalyst
Age
(years)

Design

2025

209 / 3030

05/10/12

2209

186 / 2700

05/07/13

2125

182 / 2640

Case Study 5 - Topsoe S-200 converter

Topsoe S-200 converter,

75m3 KATALCOJM 35-8/35-4 catalyst in 1998.
16 years catalyst life
10 years data shows fit quality & ability to optimise
Plant Data: 1/10/08

Circulation Rate (Nm /hr)

2
Converter Inlet. Pressure (kg/cm g)
Converter Inlet Temp (C)
Converter Exit Temp (C)
Bed 1 Inlet Temp (C)
Bed 1 Exit Temp (C)
Bed 2 Inlet Temp (C)
Bed 2 Exit Temp (C)
NH3 Exit Analysis (mol%)
Ammonia Make (MTPD)

Measured
Data
634,061
140.6
129
291
389.5
493
378
454
13.98
1144

Model Fit
Data
628,252
140.6
126
294
393
492
382
453
13.76
1144

Optimize
Data
628,252
140.6
409
512
390
460
14.03
1168

Case Study 5 - Topsoe S-200 converter

Reloaded in 2014

Bed

Volume m3

Catalyst

21.0

KATALCOJM 35-8A

57.0

KATALCOJM 35-8A

Plant data

Record make
We have broken the monthly record in the ammonia plant, it seems
the loaded ammonia catalysts are working very well

KATALCOJM 74-1

KATALCOJM 74-1
Cobalt promoter
Cobalt enters the magnetite
lattice and remains after
reduction
Increases nitrogen adsorption
Increases ammonia desorption
Increases activity

Activity increase due to

Cobalt
Unique manufacturing process
Reoptimised mix of standard
promoters

Promoters in KATALCOJM 74-series

SEM Images of 74-1

74-1 (oxidic) Fe map

74-1 (oxidic) Co map

Bulk magnetite material shows

significant cobalt incorporation
Between the magnetite grains
show no cobalt.

Cobalt enters the magnetite

lattice and remains after
reduction
Increases nitrogen adsorption
Increases ammonia desorption
Increases activity
74-1R (reduced) Fe map 74-1R (reduced) Co map

KATALCOJM 74-1- Performance

Consistently higher activity
throughout catalyst lifetime
Lower temperature reduction
Lower strike temperature
Long lifetime
The highest activity iron
catalyst available
Proven at low pressure
Proven at higher pressures

1
0.9

relative ammonia formed

0.8
0.7

74-1
0.6

Standard Magnetite
catalyst

0.5
0.4
0.3
0.2
0.1
0
350

370

390

410

Temperature C

430

450

KATALCOJM 74-1 - Stability & Longevity

User

Technology

Operating

Terra Severnside, UK (closed)

LCA 2

20 years

Puyang, Henan, China

Uhde

20 years

Terra Severnside, UK (closed)

LCA 1

15 Years

CBC, Hainan, China

Casale

19 years+

AMV

17 years +

Casale

14 years+

Incitec Pivot, Australia

KBR/Casale

13 years+

SAFCO, Saudi Arabia

Uhde

8 years+

Duslo, Slovakia

Uhde

7 years+

Saudi Mining, Saudi Arabia

Uhde

4 years+

Casale

2 years+

CF Courtright, Canada
Orica, Australia

Dyno, Australia

Worlds Largest Plants

Uhde Dual Pressure Plants

Worlds Largest Ammonia Plants

Worlds Largest Ammonia Plants

90m3 KATALCOJM 35-series

82m3 KATALCOJM 74-1 series

Above flow sheet JM catalyst in 3 radial converters

Ammonia plant with three reactors

Capacity 3300 mtpd

Uhde Dual Pressure
Process
Commissioned 2006

3 Ammonia reactors,
6 radial beds

45

Synthesis Unit of Uhde Dual Pressure Plant

3 Converters
with the Startup Heater

Plant 1
Commissioned 2006
Above nameplate at lower than design loop pressure
KATALCOJM 74 & 35 Series capable of much higher
production if more syngas is available
Make
(mtpd)

OT Inlet
Pressure
(kgf/cm2 /
psig)

Main Inlet
Pressure
(kgf/cm2 /
psig)

Design

3300

112 / 1590

212 / 3020

Feb 2012

3284

106 / 1510

206 / 2930

Apr 2013

3361

104 / 1480

199 / 2830

Plant 2
Commissioned 2011
Above nameplate at lower than design loop pressure
KATALCOJM 74 & 35 Series capable of much higher
production if more syngas is available
Make
(mtpd)

OT Inlet
Pressure
(kgf/cm2 /
psig)

Main Inlet
Pressure
(kgf/cm2/
psig)

Design

3300

112 / 1590

212 / 3020

Jun 2011

3123

99 / 1410

166 / 2360

Feb 2012

3346

100 / 1420

194 / 2760

Jan 2013

3352

101 / 1440

201 / 2860

Mar 2015

3500

102 / 1477

205 / 2985

JM ammonia synthesis

Installed in worlds largest ammonia plant

Installed in worlds most efficient ammonia plant
Installed in lowest pressure applications
Lives in excess of 20 years and still going
Installed in all types of reactor design:
Topsoe, KBR, Casale, Uhde, ICI, Braun

Never replaced due to catalyst failure

Consistently achieves above design performance
The lowest risk, highest performance, option for your plant

Thank you