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Claus process

The Claus process was discovered over 100 years ago and has been used by
industry to recover elemental sulfur from H2S bearing acid gas streams for over 50
years.
The Claus process is the most significant gas desulfurizing process, recovering
elemental sulfur from gaseous hydrogen sulfide. The overall main reaction equation is:
2H2S + O2 ↔ 2S + 2H2O
The Claus reaction is an equilibrium reaction; the extent of reaction completion
depends on the concentration of the reactants and products and operating conditions.
Because the Claus reaction is limited by equilibrium, a series of conversion
steps/stages is utilized to increase the overall conversion of H2S to sulfur.
A sulfur condenser is provided to condense and separate the sulfur formed in each
conversion stage.
The Claus Sulfur Recovery Unit (SRU) may be considered in two general sections:
1. The thermal section: in which H2S is converted to elemental sulfur at high
temperature (>1800 ºF) without the aid of catalyst.
2. The catalytic section: in which sulfur is formed at much lower temperatures (400 -
650 ºF) through the use of Claus alumina catalyst.
The Claus technology can be divided into two process steps, thermal and catalytic
Thermal step
hydrogen sulfide gas combustion at temperatures above 850°C such that elemental
sulfur precipitates in the downstream process gas cooler.
2H2S + 3O2 → 2SO2 + 2H2O (ΔH = -518 kJ mol−1)
This is a strongly exothermic free-flame total oxidation of hydrogen sulfide
generating sulfur dioxide that reacts away in subsequent reactions. The most
important one is the Claus reaction:
2H2S + SO2 → 3S + 2H2O
Side reactions
Other chemical processes taking place in the thermal step of the Claus reaction are:

I. The formation of hydrogen gas:


2H2S → S2 + 2H2 (ΔH > 0)
CH4 + 2H2O → CO2 + 4H2

II. The formation of carbonyl sulfide:

H2S + CO2 → S=C=O + H2O

III. The formation of carbon disulfide:

CH4 + 2S2 → S=C=S + 2H2S


Catalytic step
The Claus reaction continues in the catalytic step with
activated aluminum(III) or titanium(IV) oxide, and serves to boost the sulfur yield.
More hydrogen sulfide (H2S) reacts with the SO2 formed during combustion in the
reaction furnace in the Claus reaction, and results in gaseous, elemental sulfur.
2H2S + SO2 → 3S + 2H2O (ΔH = -1165.6 kJ mol−1)
The catalytic recovery of sulfur consists of three sub-steps:
• Heating
• Catalytic reaction
• Cooling plus condensation.
These three steps are normally repeated a maximum of three times. In Claus plant,
only two catalytic stages are usually installed.
Heating The first process step is the gas heating process, which is necessary to
prevent sulfur condensation in the catalyst bed, that can lead to catalyst
fouling.
The typically operating temperature of the first catalyst stage is 315°C to 330°C
(bottom bed temperature). This high temperature helps to hydrolyze COS and CS2,
which is formed in the furnace and would not otherwise be converted in the modified
Claus process.
Catalytic Reaction The catalytic conversion is maximized at lower temperatures.
The operating temperatures of the subsequent catalytic stages are typically
240°C for the second stage and 200°C for the third stage (bottom bed
temperatures).
Cooling plus condensation In the sulfur condenser, the process gas coming from
the catalytic reactor is cooled to between 150 and 130 °C. The
condensation heat is used to generate steam at the shell side of the
condenser.
Before storage, liquid sulfur streams from the process gas cooler, the sulfur
condensers and from the final sulfur separator are routed to the degassing unit,
where the gases (primarily H2S) dissolved in the sulfur are removed.