06 ammonia synthesis catalyst in action - march 2015
Post on 30-Sep-2015
21 Views
Preview:
DESCRIPTION
TRANSCRIPT
-
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)
3
Fritz Haber Patent Certificate
-
First continuous ammonia production
(1909)
4
-
Catalyst development
5
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.
Alwin Mittasch
-
Reactor development
6
Carl Bosch
Max Appl, IFA Technical Conference, September 25.-26., 1997, Sevilla,Spain
-
Reactor development
7
BASF Information, 8/1974
-
Centrifugal machines
8
-
General trends
9
0
20
40
60
80
100
120
140
0
500
1000
1500
2000
2500
3000
3500
1930 1940 1950 1960 1970 1980 1990 2000 2010
En
erg
y C
on
su
mp
tio
n
Pla
nt
Cap
ac
ity
Year of Commissioning
BASF
expertise
acquired
UHDE
becomes
partner
First
3300tpd
start-up
-
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
CaO - protects the K
promoter against
neutralisation and
increases the
stability against
poisoning by sulphur
Need to balance activity, reduction
speed and lifetime
-
KATALCOJM Ammonia Synthesis
Proven catalyst references in action
-
Proven performance - catalysts
= KATALCOJM 35-series
~36
= KATALCOJM 74-series
~8
= KATALCOJM S6-10
(equivalent to 35 series)
~19
-
Proven performance - converters
= Kellogg/KBR ~9
= Topsoe ~1
= Casale ~20
= ICI ~3
= Uhde ~24
= Other ~5
-
KATALCOJM 35 Series
-
Ammonia Synthesis
1913 converter 2015 ammonia converter
using KATALCOJM 35-8 magnetite
Images courtesy of BASF
-
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
-
1890 MTPD Plant , India
Operating around 105% of plant rated capacity
Conversion achieved per pass: 16-17% of NH3 Production details:
Case Study Revamped Kellogg converter
Year Age
(year)
Make
(MTPD)
Inlet
pressure
(kg/cm2)
May 2013 0 1965 178
Apr 2014 1 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
Converter inlet pressure barg 130 130 130
Converter inlet temperature C 179 182 185
Converter exit temperature C 433 433 441
Converter exit NH3 %(mol) 17.4 17.6 18
Ammonia make te/day 1410 1410 1438
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
-
Higher NH3 Conversion
Lower NH3 loop pressure
Case Study 1 KBR converter Asia
-
Case Study 1 KBR converter Asia
-
Make
(mtpd)
Inlet
Pressure
(barg/psig)
Catalyst
Age
(years)
Aug 2006 1474 208 / 3020 0
Jun 2008 1504 211 / 3060 2
Jul 2012 1634 209 / 3030 4
Jul 2013 1578 201 / 2910 5
Plant design 1150 mtpd, 3-bed Casale converter KATALCOJM 35-8A catalyst installed 2006 Record production achieved
Case Study 2 Casale converter UK
-
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 3 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 8
05/07/13 2125 182 / 2640 9
Case Study 4 Uhde converter MENA
-
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
Measured Data
Model Fit Data
Optimize Data
Circulation Rate (Nm3/hr) 634,061 628,252 628,252
Converter Inlet. Pressure (kg/cm2g) 140.6 140.6 140.6
Converter Inlet Temp (C) 129 126 -
Converter Exit Temp (C) 291 294 -
Bed 1 Inlet Temp (C) 389.5 393 409
Bed 1 Exit Temp (C) 493 492 512
Bed 2 Inlet Temp (C) 378 382 390
Bed 2 Exit Temp (C) 454 453 460
NH3 Exit Analysis (mol%) 13.98 13.76 14.03
Ammonia Make (MTPD) 1144 1144 1168
Case Study 5 - Topsoe S-200 converter
-
Reloaded in 2014
Bed Volume m3 Catalyst
1 21.0 KATALCOJM 35-8A
2 57.0 KATALCOJM 35-8A
Case Study 5 - Topsoe S-200 converter
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
Bulk magnetite material shows significant cobalt incorporation
Between the magnetite grains show no cobalt.
74-1 (oxidic) Co map 74-1 (oxidic) Fe map
74-1R (reduced) Fe map 74-1R (reduced) Co map
Cobalt enters the magnetite lattice and remains after
reduction
Increases nitrogen adsorption
Increases ammonia desorption
Increases activity
-
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
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
350 370 390 410 430 450
Temperature C
rela
tive a
mm
on
ia f
orm
ed
74-1
Standard Magnetitecatalyst
-
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+
-
Worlds Largest Plants
Uhde Dual Pressure Plants
-
Worlds Largest Ammonia Plants
-
90m3 KATALCOJM 35-series
82m3 KATALCOJM 74-1 series
Above flow sheet JM catalyst in 3 radial converters
Worlds Largest Ammonia Plants
-
Ammonia plant with three reactors
Capacity 3300 mtpd
Uhde Dual Pressure Process
Commissioned 2006
3 Ammonia reactors, 6 radial beds
-
page
45
Synthesis Unit of Uhde Dual Pressure Plant
3 Converters
with the Start-
up 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
top related