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Ammonia

Background information

Ammonia is one of the main products of chemical industry

(especially for fertilizers and explosives)
In the past ammonia was produced as a by-product during the
distillation of coal in coke ovens and gas works
insufficient already at the turn of the century
Ammonia production using nitrogen from the air :
Haber-Bosch process

The discovery of nitrogen fixation from air was suggested to be the

most important scientific advancement of the 20th century.

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Ammonia production in numbers

Ammonia uses
85 % of ammonia is used for nitrogen fertilizers-urea is the most
important accounting for 40% of ammonia usage
Other industrial uses include the production of nitric acid, amines,
nitriles, nylon and organic nitrogen compounds
Environmental applications removal of NOx from flue gases of
pilot plants

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Energy data for nitrogen

Value
(kJ/mol)

Compare with
(kJ/mol)

Bond dissociation energy

945

C-H in CH4: 439

Ionization energy

1503

O2: 1165

Electron affinity

34900

O2: 43

H = -91.44
-91 44 kJ/mol

Ammonia production from air

Problems:
Bond dissociation energy and electron affinity very high
activation
ti ti by
b ionization
i i ti nearly
l impossible
i
ibl
Fraction of NH3 in a 3:1 mixture of H2 and N2 at
1290 K: 0,01%
Industrial production only possible if good catalysts are found

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Haber Bosch process development

Haber and Bosch developed a process for the production of

ammonia from nitrogen in 1908 1913
Testing 6500 catalysts they discovered the high activity of iron
based catalysts.
Modern catalysts are still closely related to original ones

Thermodynamics
High pressure and low temperature are needed
At temperatures lower than 670 K the rate of the reaction is very
low
minimum temperature required to reach the equilibrium
sufficiently fast
Typical reaction conditions:
675 K at inlet; 720 770 K at outlet
100 250 bar

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Thermodynamics

Catalysts for ammonia synthesis

The iron catalyst consists of magnetite (Fe3O4) which is enriched

(promoted) most frequently with Al- and K- (or Ca, Mg, Si)-oxides.
The promoters are dissolved in the magnetite or form metal ferrites

Composition: 89-95% Fe3O4, 2-4% Al2O3, 0.5-1% K2O, 2-4% CaO

Catalyst is produced by fusing (melting) magnetite ore with the other

promoters at 1700oC and pouring melt into water to form fine particles

Iron being a transition metal with partially occupied d-bands represents a

surface suitable for adsorption and dissociation of N2 molecules
Not only iron based catalysts are active for ammonia synthesis

Os, Ru are equally active with Fe

Ru is most active in ammonia decomposition

Mo, U and Mn show quite high activity in ammonia synthesis

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Role of catalyst promoters - Poisons for ammonia synthesis

The addition of Al and K promoters drastically increases the activity
K acts as an electron donor that increases the electron density and thus
g
number of active sites on the surface
provides a higher
Al influences the morphology of the catalyst, increasing its porosity and free
surface area
Water, hydrogen sulfide and halogens are strong poisons as they adsorb
strongly on the surface
H2O causes site blocking but it is reversible
2S also blocks the surface by S* irreversibly. Large partial pressures
of H2S may cause the formation of FeS
Oxygen concentration should be kept low < 50 ppm as it is adsorbed strongly

Reduction of the catalysts

Before use, the catalyst is reduced with H2 at 500C for up to 100h
to be converted to the active structure
to provide metallic Fe
removal of oxygen makes the material porous
specific surface area increases
The promoters are in still oxidic phase after the reduction
The surface are of the reduced catalyst is around 290 m2/g

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General mechanism of ammonia synthesis

The reaction follows
a Langmuir-Hinshelwood (LH) mechanism
both reactants are dissociatively adsorbed on the surface before reaction

The dissociative adsorption of N2 is the rate determining step

Calculated reaction pathways for ammonia synthesis over

Ru catalyst

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Reactor design
Requirements to reactors:
Gas phase reactor with a solid catalyst
Temperature control as the reaction is exothermic
Two methods applied
Quench reactor in which cold gas is inserted at different
heights of the reactor
Reactor with heat exchangers between the catalyst beds

The ICI quench reactor

Part of the cold feed flows down on the outer shell of

the reactor to cool it (feature used in most converters).
It is then heated in the effluent heat exchanger
before entering the catalyst bed
One single catalyst bed containing of three zones
separated by gas distributors.

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Kellogg vertical quench reactor

Feed enters at the bottom and cools the
shell while flowing upwards
Four separated catalyst beds
Inlet of quench gas between the beds

Haldor Tops
Topse
e radicalradical-flow reactor
Main difference compared to other reactors:
radial
di l fl
flow th
through
h catalyst
t l tb
bed
d
reduces pressure drop
allows smaller particles
more catalytic area per unit volume

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Integrated ammonia plant

Pressure to improve the economy is very high

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Ammonia synthesis loop

The yield of ammonia per pass ranges between 20 and 30%
Unconverted synthesis gas leave the reactor together with
ammonia

Trends in catalysts for ammonia synthesis

TEM image of the Ba-Ru/MgO catalyst

after reduction at 783 K

Catalytic activity of
a)the bari
barium-promoted
m promoted catalyst
catal st (Ba
(Ba-Ru/MgO),
R /MgO)
b) the cesium-promoted catalyst (Cs-Ru/MgO),
c) the industrial iron catalyst,
d, e) unpromoted Ru/MgO catalysts (Ru/MgO),
f) ammonia mole fractions at equilibrium

M. Muhler, O. Hinrichsen Angew. Chem. 2001

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