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Sulfuric acid
Large volume chemical, > 130 million t/a
Applications: fertilizers, refining (alkylation process), paper
industry, recovery of Cu, U, V
Produced by catalytic oxidation of SO2 and consecutive absorption
of SO3 in diluted sulfuric acid
Sources for SO2 are sulfur, spent sulfuric acid (diluted,
contaminated) and H2S
Acid strength ranges from 33 to 114 wt% (oleum: wt%SO3
dissolved in 100wt%H2SO4).

Process development of H2SO4 production

18th and 19th century

1920

Lead Chamber process

Liquid phase
vanadia catalysis

1960
Double absorption process

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Reactions and Thermodynamics

Formation of SO2 by oxidation of sulfur

(combustion with air)
Catalytic oxidation of SO2 to SO3

Absorption
p
of SO3 in water

As all steps are exothermic, low temperatures favor equilibrium

conversion but the rates of reactions are slow.

Process scheme
Lowest viscosity
410-425 K

690 K

Steam production (40 bar, 400C) : 1.3 t/t H2SO4

Heat capacity: 63 MW for 1000 t H2SO4 /day

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Details of the Process

Molten sulfur is combusted in dry air to SO2 at 900C; H2SO4 is
used for air-drying.
After cooling
g down, the mixture of 10% SO2 in air ((waste heat
boiler) it passes through a hot gas filter and then enters the first
catalyst bed.
Since pressure drop is quite a problem, the first bed is of large
diameter (3 m) and very shallow
After 4th bed; conversion of SO2 is 98.5% at maximum;
environmental aspects require an even higher conversion of SO2
beyond equilibrium.
Double absorption process: 90% of SO3 is absorbed in H2SO4
after third converter; for constant acid concentration water needs to
be added at 80C before further conversion at 410C.

Generation of SO2
Combustion of sulfur with excess air from SO2
oxidation; generated SO2 needs cooling before further
oxidation
id ti
Metallurgy produces SO2 containing waste gases
which need stripping and electrostatic purification
before conversion into SO3
Spent acid regeneration (SAR): Sulfuric acid and
waste H2S are decompressed at high temperatures,
cooled and dried
dried. Further conversion into SO3 is
temperature dependent.

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Oxidation of SO2

Adiabatic increase of temperature in catalyst bed

Optimal temperature ranges from 410 to 440C, compromise

between maximum conversion and an acceptable rate of reaction.

Oxidation of SO2

T/C X/%

Single absorption adiabatic

fi d b
fixed
bed
d reactor
t

440
600 63,0
450
510 87,0
450
470 94,5
425
435 98,0

Conversion: 98-99%

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Absorption of SO3
Due to high exothermicity it is
impossible to absorb SO3 directly
i H 2O
in
Removal of SO3 by absorption in
98% H2SO4 allows conversion
beyond thermodynamic
equilibrium.
Intermittent cooling is yet very
expensive

Lead chamber process

Oldest process: developed in 1746 by John Roebuck, applied in the

18th and 19th century
Homogenous catalysis with nitrogen oxides, the acid is condensed in a
l d chamber.
lead
h b

As Ciba-Geigy-Process still used for gases with low SO2 content

Maximum H2SO4 concentration is 78 %; higher concentrations require

large energy input.

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Modern catalyst systems

Pd on asbestos -very sensitive to poisoning by heavy metals
Robust catalysts mostly used are sulfated K2O/V2O5 with Na/ Cs
additives on silica surface; 6-9wt.% V2O5 15-25wt.% K2O/Na2O.
In the working catalyst the active catalytic phase exists as molten salt
dimer with oxygen bridge
The exact structure is not known.

Haldor Topsoe V/K catalyst

Catalytic mechanism and kinetics

Mars van Krevelen mechanism
SO3 absorption on surface is preferred to SO2 absorption
Activation energy is extremely temperature dependent; below
420C precipitation of inactive vanadium compounds rises Ea to
200-280 kJ/mol; above: Ea = 60-90 kJ/mol

Mechanistic proposal
breaking the V=O bond

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Kinetic studies by Dunn et al

Formation and desorption of SO3 in the gas phase is the rds

J. Dunn et al., Appl. Catal. B, 19 (1998) 103

Breaking temperature of the vanadia species

Bend in Arrhenius plot for different alkali additives indicates

change in the mechanism at higher temperatures.

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Deactivation of the catalyst

Below the break temperature of 400-430C conversion of VV into
inactive species VIV, VIII and precipitation might cause a sudden drop in
catalytic activity; process can be reversed upon heating
heating.
Mechanical degradation predominant in the first bed due to high reaction
temperatures, dust in incoming gas stream leads to fouling.
High temperatures favor sintering and loss of volatile active vanadium
species.
Poisoning by As and F containing compounds
However: usual life times are up to 20 years

Improvements
Addition of Cs oxides to conventional V catalyst lowers break
temperature below 400C
Catalysts
C t l t with
ith smallll pores and
d hi
high
h surface
f
area h
have Tbreak<
375C (wet flue gas).
Catalyst shape influences pressure drop in first bed; daisy shape is
the state of the art.
Air cooling instead of water cooling.
Maximization of oleum production.

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Structure of the catalyst system

Cs impregnated V2O5/SiO2 catalyst

Giakoumelou et al., J.Cat. 225, 2004, 337.