Claus process

The Claus process is a catalytic chemical process that is used for converting gaseous
hydrogen sulfide (H2S) into elemental sulfur (S).[1] [2] [3] The process is commonly
referred to as a sulfur recovery unit (SRU) and is very widely used to produce sulfur
from the hydrogen sulfide found in raw natural gas and from the by-product sour
gases containing hydrogen sulfide derived from refining petroleum crude oil and other
industrial facilities.
There are many hundreds of Claus sulfur recovery units in operation worldwide. In
fact, the vast majority of the 68,000,000 metric tons of sulfur produced worldwide in
2010 was by-product sulfur from petroleum refining and natural gas processing
plants.[4]

Feed gas composition

Claus unit feed gases have a wide range of compositions. Most of the feed gases are
originate from absorption processes using various solvents to extract hydrogen sulfide
from the by-product gases of petroleum refining, natural gas processing, tar sands
processing, coal gasification, smelters, coke ovens and other industries. The
absorption processes used for that purpose include Amine gas treating, Rectisol and
Selexol to name a few.
In addition to hydrogen sulfide extracted from by-product gases by an absorption
process, petroleum refineries also derive hydrogen sulfide from the steam distillation
of wastewaters containing dissolved hydrogen sulfide. Those wastewaters are referred
to as sour water and the steam distillation of those wastewaters is referred to as sour
water stripping.
The table below provides typical analyses of the Claus feed gases obtained from
amine gas treating and from sour water stripping:

Gases with an H2S content of over 25% are suitable for the recovery of sulfur in
straight-through Claus process units (as described in the next section). Other process
design configurations can be used to handle gases with lesser amounts of H2S.[5]
The amount of hydrogen sulfide derived from sour water stripping in a petroleum
refinery is very much less than is derived from the refinery's amine gas treating
facilities.

Schematic flow diagram and description

A Claus process plant

The Claus reaction to convert H2S into elemental sulfur requires the presence of one
mole of SO2 for each two moles of H2S:

(1) 2H2S + SO2 3S + 2H2O

To provide that ratio of components, the first step in the Claus process is the
combustion of one-third of the H2S in the feed gas:

(2) H2S + 1.5 O2 SO2 + H2O

Combining equations (1) and (2), the overall process reaction is:

(3) 2H2S + O2 2S + 2H2O

As shown in the schematic diagram below, the feed gas to a Claus process unit is
burned in a reaction furnace using sufficient combustion air to burn only one-third of
the H2S it contains. That is accomplished by using a flow ratio controller to provide
the required ratio of combustion air to feed gas.
The reaction furnace pressure and temperature is maintained at about 1.5 bar gauge
(barg) and about 1,000 C. At those conditions, the Claus reaction occurs thermally in
the reaction furnace (i.e., without requiring any catalyst). About 70% of the H2S in the
feed gas is thermally converted into elemental sulfur in the reaction furnace.
The hot reaction product gas, containing gaseous sulfur, is used to produce steam in a
boiler (called a waste heat boiler) which results in cooling the gases. The gas is then
further cooled and condensed in a heat exchanger while producing additional steam.
The condensed liquid sulfur is separated from the remaining unreacted gas in the
outlet end of the condenser and sent to product storage.
The separated gas is then reheated and enters the first catalytic reactor maintained at
an average temperature of about 305 C where about 20% of the H2S in the feed gas is
converted into elemental sulfur. The outlet product gas from the first reactor is cooled
in another condenser while also producing steam. Again, the condensed liquid sulfur
is separated from the remaining unreacted gas in the outlet end of the condenser and
sent to product storage.
The separated gas from the second condenser is sent to another reheater and the
sequence of gas reheat, catalytic reaction, condensation and separation of liquid sulfur
from unreacted gas is repeated for the second and third reactors at successively lower
reactor temperatures. About 5% and 3% of the H2S in the feed gas is thermally
converted into elemental sulfur in the second reactor and third reactors, respectively.
For a well-designed and operated Claus sulfur recovery plant having three catalytic
reactors (as shown in the flow diagram), an overall conversion of at least 98% can be
achieved. In fact, the latest modern designs can achieve up to 99.8% conversion of
hydrogen sulfide into product sulfur that is 99+% saleable "bright yellow sulfur".
The remaining gas separated from the last condenser is referred to as "tail gas" and is
either burned in an incinerator or further desulfurized in a "tail gas treatment unit"
(TGTU).

Reheat methods
The various methods used for the reheating required upstream of each catalytic
reactor include:

Direct gas-fired heaters using fuel gas and designed to operate at substoichiometric conditions to prevent any oxygen (O2) from getting into the
reactors which can damage the catalyst.

Gas-to-gas heat exchangers in which cooled gas from a condenser exhanges

heat with the hot gas from the upstream reactor.

Steam-to gas heat exchangers in which the cooled gas from a condenser is
heated with high-pressure steam.

Other design features

Older Claus sulfur recovery units were designed using only two catalytic reactors.
Such units will typically convert only about 97% of the H2S in the feed gas. Because
of stringent environmental regulatory requirements in the United States as well as
many other nations, many of those older units have been upgraded to include three
reactors. The tail gas from those that have not been upgraded is very probably
desulfurized further in a tail gas treatment unit.
When the feed gas to a Claus unit includes ammonia and hydrocarbons (such as in the
overhead gas from a petroleum refinery sour water stripper), special designs of the
reaction furnace burner are available to provide complete combustion of those feed

gas components.
To obtain higher reaction furnace temperatures and/or reduce the gas volume to be
processed, pure oxygen may be used to enrich the reaction furnace combustion air.

Catalyst
The catalytic reactors each contain a bed of catalyst with a depth of about 90 to 120
cm. The most widely used Claus reaction catalyst is porous aluminum oxide (Al2O3),
commonly referred to as alumina.[6] [7]
The alumina catalyst owes its activity to a very high surface area of 300 m/g or
higher. About 95 % of that surface area is provided by pores having diameters of less
than 8 nm (80 angstroms).
The catalyst not only increases the kinetics (i.e., the rate of reaction) of the Claus
reaction equation (1), but it also hydrolyzes the carbonyl sulfide (COS) and carbon
disulfide (CS2) that is formed in the reaction furnace:

(4) COS + H20 H2S + CO2

(5) CS2 + 2H20 2H2S + CO2

The H2S formed as per the hydrolysis equations (4) and (5) is then converted into
elemental sulfur as per the Claus reaction (1). Most of the hydrolysis occurs in the
first Claus reactor.
Other Claus catalysts based on titanium dioxide (TiO2) are also used. The titanium
dioxide catalysts are produced from anatase, one of the three naturally occurring
mineral forms of titanium dioxide. They are also called titania catalysts and are said
to be more resistant to thermal aging than the alumina catalysts. They are also said to
have a higher activity for the hydrolysis of COS and CS2 which allows the first Claus
reactor to operate at lower temperatures compared to alumina catalysts.[8] However,
they are significantly more expensive than the alumina catalysts.

History
In nineteenth century, there were many alkali manufacturing plants in England
producing sodium carbonate (Na2CO3) by the Leblanc process. The original Claus
process was developed by Carl Friedrich Claus, a chemist working in England, for the
purpose of recovering sulfur from the waste calcium sulfide (CaS) generated by the
Leblanc process. As a catalyst, he chose a bog iron ore and later bauxite (a mineral
with a high alumina content).[9] In 1883, Claus was granted a British patent for the
process.[10] [11] [12]

During the next 53 years, the Claus process underwent several minor modifications.
In 1936, I.G. Farbenindustrie a (German conglomerate of chemical companies)
introduced a modification of the process that utilized a thermal conversion step
followed by catalytic conversion steps, which is the basically the concept currently
used in modern Claus sulfur recovery units