Improved Efficiency in Ammonia Synthesis: John Brightling October 2015

Improved efficiency in ammonia synthesis
John Brightling
October 2015
Agenda
• Introduction and history

• Catalyst Chemistry
• Proven references in action
• KATALCOJM 35-4
• KATALCOJM 74-1
• Worlds largest plants
• Performance in Dual Pressure Process
© Johnson Matthey 2015

Loop for ammonia production
Fritz Haber - Chemical Engineer
Fritz Haber Patent Certificate

First continuous ammonia production
(1909) – using a loop
Catalyst development
Alwin Mittasch - Catalyst Chemist
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 - Mechanical Engineer
Carl Bosch
Max Appl, IFA Technical Conference, September 25.-26., 1997, Sevilla,Spain

1913 BASF development team
Process
Haber
Chemical Mechanical
Mittasch Bosch
Lead to an integrated process

Reactor development
BASF Information,
8/1974
General trends
3500 140
3000 First
BASF
UHDE 120
3300tpd
expertise
becomes
2500 start-up
acquired
partner 100
Energy consumption
Plant capacity
2000 80
1500 60
1000 40
500 20
0 0
1930 1940 1950 1960 1970 1980 1990 2000 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
• KATALCOJM 74-1 series

catalyst
• AMV process
• LCA Process
• Dual Pressure Process
• Highest activity Iron based
catalyst in the World

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 stabilizers
Promoter Effect
AI2O3 Stabilizes 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
neutralization 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

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.

Case study 1 – KBR converter Asia

• 1350mtpd Kellogg - 2 bed inter-cooled horizontal beds

Higher NH3 conversion
Lower NH3 loop pressure


Case study 2 – Casale converter UK
• Plant design 1150 mtpd, 3-bed Casale converter

• KATALCOJM 35-8A catalyst installed 2006
• Record production achieved, good stability
Make Inlet Catalyst

(mtpd) Pressure Age
(barg/psig) (years)
Aug 2006 1474 208 / 3020 0

Jun 2008 1504 211 / 3060 2
Jul 2012 1634 209 / 3030 6
Jul 2013 1578 201 / 2910 7
Sept 2015 1590 206 / 2990 9

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 Inlet Catalyst
(mtpd) Pressure Age
(barg/psig) (years)
Design 1200 190 / 2760

Sep 2012 1206 181 / 2625 14
Mar 2013 1206 179 / 2595 15

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
• Reoptimized mix of standard
promoters

Promoters in KATALCOJM 74-series
74-1 (oxidic) Fe map 74-1 (oxidic) Co map
• SEM Images of 74-1
• 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 1
0.9
• Proven at higher pressures 0.8
relative ammonia formed

0.7
74-1
0.6
Standard Magnetite
0.5 catalyst
0.4
0.3
0.2
0.1
0
350 370 390 410 430 450
Temperature °C

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+
CF Courtright, Canada AMV 17 years +
Orica, Australia 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+
Dyno, Australia Casale 2 years+

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+
CF Courtright, Canada AMV 17 years +
Orica, Australia 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+
Dyno, Australia Casale 2 years+

Case study 4: Casale Revamp
• Ammonia Plant 800mtpd

• KBR 4th bed booster converter
installed in 1997
• Used KAAP catalyst Ru on
activated carbon substrate
• KAAP catalyst rapidly degraded
resulting in a loss of activity, loss
in plant capacity and loss of
catalyst from the reactor
• Reactor converted by Ammonia
Casale to use KATALCOJM 74-1

Case study 4 : Casale revamp

Case study 4 : 4th Bed duty
N2+3H2 2NH3
Ru
Reaction Rate
Fe
N2+3H2 2NH3
Ammonia %
Relative Inhibition of
Ru and Fe Catalyst
Ammonia, Appl 1999

New large plants
• 2200mtpd TKIS Uhde – 2 converter 3 bed, inter-bed HP boiler
HP steam
Refrigeration
Purge
C.W.
NH3
( liquid )
BFW
Make-up gas
Syngas compressor

New large plants
• 2200mtpd TKIS Uhde – KATALCOJM 74-1 in Bed 2 and 3,
HP steam
Additional
Loop pressure
production
can of
be25,000te/year
reduced 4%
Refrigeration
Purge
C.W.
NH3
( liquid )
BFW
Make-up gas
Syngas compressor

World’s largest plants
Uhde Dual Pressure Plants

World’s largest ammonia plants

World’s largest ammonia plants
90m3 KATALCOJM 35-series
82m3 KATALCOJM 74-1 series
Above flow sheet JM catalyst in 3 radial converters

Case study 5: Saudi Arabia
• Capacity 3300 mtpd
• Uhde Dual Pressure

Process
• 3 Ammonia reactors,
6 radial beds plus a
start-up heater

Case study 5: Plant performance
• Commissioned 2011
• Above nameplate at lower than design loop pressure
• KATALCOJM 74 & 35 Series capable of much higher
production if more syngas was available
Make OT Inlet Main Inlet
(mtpd) Pressure Pressure
(kgf/cm2 / (kgf/cm2/
psig) 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 world’s largest ammonia plant

• Installed in world’s 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

Improved efficiency in ammonia synthesis
John Brightling
October 2015

Improved Efficiency in Ammonia Synthesis: John Brightling October 2015

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Improved efficiency in ammonia synthesis

• Introduction and history

© Johnson Matthey 2015

Fritz Haber Patent Certificate

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

Lead to an integrated process

© Johnson Matthey 2015

• Long history in ammonia

• KATALCOJM 74-1 series

© Johnson Matthey 2015

© Johnson Matthey 2015

• Magnetite (Fe3O4) precursor

© Johnson Matthey 2015

Need to balance activity, reduction

Proven catalyst references in action

Images courtesy of BASF

1913 converter 2015 ammonia converter

• Generically called “conventional magnetite”

Accelerated laboratory tests;

© Johnson Matthey 2015

© Johnson Matthey 2015

• 1350mtpd Kellogg - 2 bed inter-cooled horizontal beds

© Johnson Matthey 2015

Higher NH3 conversion

Lower NH3 loop pressure

© Johnson Matthey 2015

© Johnson Matthey 2015

• Plant design 1150 mtpd, 3-bed Casale converter

Make Inlet Catalyst

Aug 2006 1474 208 / 3020 0

© Johnson Matthey 2015

• Capacity: 1200 mtpd

• One Ammonia reactor

© Johnson Matthey 2015

• Commissioned Oct 1998

Design 1200 190 / 2760

© Johnson Matthey 2015

© Johnson Matthey 2015

• Cobalt enters the magnetite

74-1R (reduced) Fe map 74-1R (reduced) Co map

© Johnson Matthey 2015

• Consistently higher activity

relative ammonia formed

© Johnson Matthey 2015

User Technology Operating

Puyang, Henan, China Uhde 20 years

Terra Severnside, UK (closed) LCA 1 15 Years

CBC, Hainan, China Casale 19 years+

CF Courtright, Canada AMV 17 years +

Orica, Australia 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+

Dyno, Australia Casale 2 years+

© Johnson Matthey 2015

User Technology Operating

Puyang, Henan, China Uhde 20 years

Terra Severnside, UK (closed) LCA 1 15 Years

CBC, Hainan, China Casale 19 years+

CF Courtright, Canada AMV 17 years +

Orica, Australia Casale 14 years+

Incitec Pivot, Australia KBR/Casale 13 years+