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Ammonia Synthesis Catalyst (VSG-A101)

Chemistry and Operator Training






by:
Gerard B. Hawkins
Managing Director, CEO


















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Technology - Methanol Catalysts / process Technology Petrochemicals Specializing in the Development & Commercialization of New
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VSG-A101 Ammonia Synthesis Chemistry and Catal ysis


Reaction stoichiometry and thermodynamics
Ammonia synthesis catalyst fundamentals
Molecular mechanism and kinetics
Activation and deactivation
Alternative catalyst technologies


Reaction stoichiometry and thermodynamics

NH
3
synthesis reaction

N
2
+3 H
2
2 NH
3
DH
700K
=- 52 kJ /mol

Equilibrium position favors NH
3
synthesis at

High pressure
Low temperature

Pressure depends on capital and operating cost

Temperature depends on the balance of kinetics/equilibrium

P & T also depend on available catalyst activity



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0
5
10
15
20
25
30
35
40
50 75 100 125 150
Pressure bara
N
H
3

c
o
n
c
e
n
t
r
a
t
i
o
n

%
380 C
400 C
420 C











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VSG-A101 Ammonia synthesis catal yst fundamentals

VSG-A101 Ammonia Synthesis Catal yst - Formulation

Based on magnetite (Fe
3
O
4
) precursor

Defined form and crystal structure

Magnetite requires controlled reduction

Pre-reduction or in situ reduction

Oxygen is removed from the crystal lattice without shrinkage

Produces extremel y porous metallic iron structure

Key in achieving a high activity catal yst

Promoters boost catal yst performance


VSG-A101 Ammonia Synthesis Catal yst - Requirements

High catal yst activity

Low sensitivity to catal yst poisons

High thermal resistance

Reasonable reduction time

High mechanical strength and abrasion resistance



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VSG-A101 Ammonia Synthesis Catalyst - Production

Unique manufacturing process

Catal yst is not made via pelleting or extrusion

Components are mixed including promoters

Feed is melted in an electric arc furnace

Solidified melt is milled to give required shape and size distribution

Melt conditions are key to produce required Fe
3
O
4
precursor phases and
morphology





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Catalyst Type

Vulcan VSG-A101
Comp J Comp J Comp H Comp H
Fe
0.5 - 0.6 - 80 - 80
Fe3O4
67 - 69.5 95 12 - 13 94.5 ~10
Al2O3
2.2 - 2.6 2.5 3.3 2.1 2.8
CaO
1.4 1.8 2 2.5 1.5 2
K2O
0.6 - 0.8 0.8 1 0.6 0.8
SiO2
< 0.5 0.25 0.3 <0.2 <0.2
MgO
- 0.25 0.3 - -
Co
- - 1 1.3
Cl
<0.0001 <0.001 <0.001 <0.001 <0.001
S
<0.0001 <0.001 <0.001 <0.001 <0.001


VSG-A101 Ammonia Synthesis Catal yst - Incorporation of Promoters

Certain metal oxides promote activity and improve stability

Small and controlled amounts

Al umina and potash are the most important

Al
2
O
3
is a structural promoter

Restricts growth of iron crystallites during reduction and operation

Increases thermal stability

Al kali metals are electronic promoters

Greatl y increase activi ty of the iron particles

K particularly effecti ve

Other promoters include CaO, SiO
2



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Contaminants in the magnetite raw material

Must be considered and controlled during manufacture

Ensures optimum concentration of promoters

Ammonia Synthesis Catal yst - Effect of Promoters and Stabilizers

Al
2
O
3
- stabilizes the internal surface

SiO
2
- stabilizes activity in presence of oxygen compounds during normal
operation and reduction

K
2
O - increases intrinsic activity of Fe particles

CaO - protects the K promoter against neutralization and increases the stability
against poisoning by sulfur


Typical Operating Conditions

Temperature 360 - 530C (680 986F)

Pressure 100 - 600 bara

Space velocity 1000 - 5000 hr
-1

Poisons limits

Oxygen and oxygen compounds normally 3 ppmv





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Typical Converter Temperatures



Converter Heat Recovery

Heat recovered is that available from synthesis exotherm across synthesis beds

Catal yst bed temperatures usuall y similar

Bed 1 410 520C T = 110 C

Bed 2 415 480C T = 65 C

Bed 3 410 450C T = 40 C

Total Bed T = Converter T = 215 C



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VSG-A101 Ammonia Synthesis Chemistry

Reaction Progress across Beds



VSG-A101 Ammonia Synthesis Catal yst - Effect of Size on Activity

Smaller pellets have higher activity

Reaction is subject to diffusion limitations

Film diffusion and pore diffusion effects

Thus, smaller means higher production (closer ATE) or lower catal yst volume

But higher pressure drop

use either axial-radial or radial flow beds to minimize

Basis of many converter internal retrofits





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VSG-A101 Ammonia Synthesis Catal yst - Effect of Size on Activity



Ammonia Synthesis Catal yst - Catalyst Size Options

Size Grade Size
A 1.5 - 3.0 mm
B 3.0 - 4.5 mm
C 3.0 - 6.0 mm
D 6.0 - 10.0 mm
G 14.0 - 20.0 mm





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Molecular mechanism and kinetics

Ammonia Synthesis Mechanism

Dissociative adsorption of H
2

Dissociative adsorption of N
2
- believed to be the Rate Determining Step (RDS)

Multi-step hydrogenation of adsorbed N
2
Desorption of NH
3
















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Ammonia Synthesis Kinetics

Detailed studies on intrinsic reaction rate

Influential work by Temkin et al.

Actual rate subject to diffusion limitations

Film diffusion and pore diffusion effects


Activation and deactivation

Catal yst Reduction

Depends on catal yst type

E.g. pre-reduced or oxide form

E.g. VSG-A101, Comp H, Comp J

Raise T in first bed to 350C* (300C
#
), then slowl y upwards @ 10C/h

Control exit H
2
O level

Maintain downstream beds at 350C* (300C
#
)

NH
3
synthesis initiates as the catal yst reduces

Once H
2
O falls, heat 2
nd
bed and repeat



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VSG-A101 Deactivation Background

Temperature

Re-crystallization of iron surface occurs slowly

Thermal sintering process

Minimize operating temperature

Commensurate with maintenance of conversion






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VSG-A101 Deactivation - Common Poisons

Oxygenated species (H
2
O, CO, CO
2
)


Converted to H
2
O

Sintering/re-organization of catal yst surface

Temporary

Low level/short duration (days)

Permanent

High levels/weeks to months

Sulfur

Incorporation of Ca promoter enhances stability of catal yst

Arsenic, Antimony and Phosphorus

Chlorine

Formation of volatile metal chlorides

Lead to KCl formation and loss of K from catal yst

Physical foulants (Fe scale, etc)




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Summary

Thermodynamics, kinetics and reaction mechanism considered

Features of ammonia synthesis catal ysts

Acti vation and deactivation parameters discussed

Brief consideration of non-Fe based commercial catal yst