06 Ammonia Synthesis Catalyst in Action - March 2015

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


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


Capacity: 2000 mtpd

Commissioned 2004

Two Ammonia reactors

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


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


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

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

Documents

06 Ammonia Synthesis Catalyst in Action - March 2015