Sulfur recovery further improved

Over 100 years ago, the original Claus process for the production of
elemental sulfur from H2S and air was introduced to the industry. In
1938, a major improvement was made by I.G. Farben through the
introduction of the free-flame thermal stage. This improved or
modified Claus Process enabled the application of the original Claus
process on a large industrial scale, making it the major process for
producing sulfur in the world.
The recovery performance of the modified Claus process is
unfortunately

limited

to

97

98%,

due

to

thermodynamic

equilibrium constraints.
In 1988, Comprimo/Gastec announced the SUPERCLAUS process,
which increased the capability of the Claus efficiency to typically
98.5 - 99.3% by introduction of selective oxidation technology to
overcome the Claus equilibrium limitations.
Fourteen years after the successful introduction of SUPERCLAUS,
more than 110 units are under license. All units in operation have
met or exceeded the guaranteed recovery efficiency. SUPERCLAUS
is now a well proven technology. However, to cope with future
requirements, the sulfur recovery efficiency needs to be increased
to 99.5% or higher.
A detailed review of the process has been made, and a significant
performance increase in the process appears to be possible if the
SO2 in the Claus process gas to the selective oxidation reactor could
be converted to S or H2S by hydrogenation, using the hydrogen
present in the Claus process gas. In addition, the control of the
selective oxidation reactor has been improved, to obtain a higher
sulfur yield in the reactor.
An improved SUPERCLAUS process has been introduced, called
EUROCLAUS. The improvement is characterized by the catalytic

reduction of SO2 in Claus process gas, by hydrogenation to sulfur

vapor and hydrogen sulfide prior to selective oxidation.
One configuration, with a small layer of hydrogenation catalyst in
the bottom of the second Claus reactor, is very attractive.
Consequently a separate reactor stage for hydrogenation is not
required with this process configuration.
Reduction of SO2 increases the performance of the final selective
oxidation stage, resulting in an overall recovery efficiency of 99.5%
or better with only three catalytic stages.
EUROCLAUS is a fully continuous Claus type sulfur recovery
process, based on bulk sulfur production by a Claus section,
selective hydrogenation of SO2 and selective oxidation of H2S.
The Claus process
A typical Claus plant flow sheet consists of a thermal stage followed
by two or three catalytic stages. In the thermal stage, which consists
of a burner with a combustion chamber and a waste heat boiler, the
H2S present in the Claus feed gas is combusted to sulfur according
to:
H2S + 0.5 O2 1/n Sn + H2O

(1)

Part of the sulfur reacts with the formed H2O to form H2S and SO2
according to the reversed Claus equilibrium reaction:
3/n Sn + 2 H2O 2 H2S + SO2

(2)

The downstream catalytic reactor stages further increase the

conversion to sulfur. A catalytic Claus stage consists of a reheater,
catalytic reactor and sulfur condenser. Condensation of sulfur after
each Claus reactor makes further production of sulfur possible in the
next catalytic stage (Figure 1).
Claus plant limitations
The theoretical sulfur recovery efficiency may be calculated as 96%
and 98% for a two and three stage Claus plant respectively. In

reality,

the

long

term

average

recovery

experienced

is

approximately 94 - 97%.
Apart from lower values caused by deactivated Claus catalyst, the
basic Claus process has three major limitations that hinder the
process for meeting higher sulfur recoveries:
Thermodynamically limited conversion to sulfur. Increase in water
vapor content and a simultaneous decrease of H 2S and SO2
concentrations in the gas.
Sensitive air to acid gas control.
Because the Claus reaction is thermodynamically limited, the
conversion to sulfur is not complete, and distinct quantities of H 2S
and SO2 remain in the process gas. Water produced by the Claus
reaction increases proportionally with the overall conversion of H 2S.
This process water hinders the conversion to sulfur and limits the
total sulfur recovery.
In all modified Claus processes, the principal control variable is the
air to acid gas ratio. The plant efficiency is quite dependent on the
two components H2S and SO2 being in the correct ratio for the
reaction. The optimum conversion to sulfur will occur at a H 2S:SO2
ratio of 2:1 .
It is clear that, notwithstanding the fact that modern Claus plants
are equipped with H2S/SO2 tail gas analyzers to control the air
demand, the process control is sensitive and easily affects the sulfur
recovery efficiency.
The concept

The concept applies two main principles to overcome the limitations

of the Claus process:

Selective oxidation of H2S directly into elemental sulfur.

More flexible air to acid gas control.

For selective oxidation of H2S to sulfur, new catalysts have been

developed because available commercial oxidation catalysts are all
sensitive to water and establish the Claus reaction.
The developed catalysts possess some unique properties:

Oxidation of more than 85% of H2S to elemental sulfur in the

presence of excess air; further oxidation to SO2 is minor.

Not sensitive to water.

The introduction of selective oxidation H2S with these catalysts in

the Claus process contributes to a significant increase in sulfur
recovery. Moreover, the catalysts allow less stringent selective
oxidation air control, as the last reactor containing the selective
oxidation catalyst can now be operated with excess air.
The Process
The process uses simple conventional Claus plant equipment and
can be applied in either existing or new plants to increase overall
sulfur recovery at low costs. It consists of a thermal stage followed
by two or three catalytic reactor stages (Figure 2).
Reactors 1 and 2 are loaded with conventional Claus catalyst, while
reactor 3 is filled with the selective oxidation catalyst, often called
the SUPERCLAUS catalyst. In the process, the exact H 2S:SO2 ratio
control of 2:1 has been abandoned. The front of the Claus plant is
operated with excess H2S in such a way that the H 2S concentration
in the tail gas leaving the last Claus reactor will contain 0.8 - 1.2 vol
% H S. The excess H S results in the additional advantage that the
Claus catalyst is rejuvenated continuously, keeping the Claus
catalyst very active and the sulfate content low.
The combustion air to the unit is split into two streams. The major
part is directed to the H2S burner of the thermal stage, the
remainder is added to the Claus process tail gas.

The presence of the excess H2S suppresses the SO2 concentration in

the gas. The tail gas leaving the second or third Claus reactor stage
is reheated, mixed with excess air and passed to the selective
oxidation reactor. Here, the non equilibrium reaction takes place:
H2S + 0.5 O2 1/n Sn + H2O
(1)
As the selective oxidation catalyst does not promote the reverse
Claus reaction of the formed sulfur vapor with water vapor, and only
minor amounts of SO2 are formed, the selectivity to sulfur is high.
The catalyst only oxidizes H2S; other components in the tail gas such
as H2, CO, SO2, COS and CS2 are not converted. Therefore, COS and
CS2 should be decreased to as low a level as possible before
entering the reactor. This can be achieved by applying the
appropriate catalyst and temperature level in the first Claus reactor.
The selective oxidation reactor is followed by a sulfur condenser to
remove the sulfur formed in this step. In order to keep sulfur vapor
losses low, the last sulfur condenser should run at an outlet
temperature of 125 C. With one thermal stage and two catalytic
Claus stages upstream of the selective oxidation stage, the overall
recovery is typically 99.2% for a rich Claus feed gas. With three
catalytic Claus stages upstream, an overall recovery up to 99.4% is
achievable.
SUPERCLAUS catalyst
The first generation SUPERCLAUS catalyst has been developed
based on a carrier of alpha alumina (-AI2O3), which has a very low
Claus activity. Very finely divided iron oxide (Fe 2O3) is coated on the
-AI2O3 surface. A small quantity of chromium oxide (Cr 2O3) is used
to stabilize the iron oxide. The advantage of this catalyst is that the
thermal stability is excellent.

This catalyst has a very low surface area of approximately 10 m 2/g,

which results in a relatively high `kindling' temperature (reactor
inlet temperature) of 240 - 250 C.
As alumina supports with higher surface areas usually contain
gamma alumina (-AI2O3), a material that is very Claus active, other
support materials such as silica carriers were investigated. Silicas
with the correct pore structure also exhibit a very low Claus activity.
A second generation catalyst, based on a silica carrier, was then
developed. It transpired that this catalyst, with a surface area of
approximately 90 m2/g, maintained a high catalytic activity without
the requirement of an additional quantity of Cr2O3. The reactor inlet
temperature

could

be

lowered

to

200

220C,

with

the

corresponding lower utility consumption.

This much lower inlet temperature meant that the average catalyst
bed temperature could be lowered, which had a very favorable
influence on sulfur yield. The sulfur yield is defined as the
percentage of incoming H2S that is converted to elemental sulfur.
A third generation catalyst is promoted with Na 2O. This promoter
decreases the SO2 formation, especially at the higher temperatures
in the bottom part of the catalyst bed.
A fourth generation catalyst contains Zn as a promoter to further
decrease the SO2 formation at the higher temperatures. This results
in a sulfur yield that is higher, and less sensitive to higher reactor
temperatures. Commercial production of this catalyst is now being
considered, to increase sulfur yields of commercial reactors, this in
view of the EUROCLAUS option.
Plant limitations
The conventional SUPERCLAUS process can attain recovery
efficiencies up to the range of 98.5 - 99.4%,' depending on the acid
gas feed quality and number of catalytic stages.

In the selective oxidation reactor (SUPERCLAUS reactor), H 2S is

oxidized to sulfur vapor according to:
H2S + 0.52O 1 /n Sn + H2O
(1)
Only H2S is oxidized. The SO2 passes through the catalyst
unaffected. This means that the SO2 concentration in the Claus tail
gas (feed to the SUPERCLAUS reactor) should be low, to limit
recovery losses. This can be achieved by an increase of H 2S content
in the Claus tail gas to approximately 1 vol%, as is done in the
SUPERCLAUS process.
SO2 is suppressed according to the Claus equilibrium:
2 H2S + SO2 3/n Sn + 2 H2O

(3)

by applying an excess of H2S.

More than 1 vol% of H2S will not increase the sulfur recovery further,
because it will result in too high a bottom temperature in the
reactor, and consequently more SO2 formation and a lower sulfur
yield of the incoming H2S in this reactor.
The SO2 concentration in the Claus tail gas under these conditions
still represents significant recovery losses. For instance, at 0.82 vol
% H2S inlet concentration, the SO2 content in the Claus tail gas is still
0.08 vol%, corresponding with 0.3% recovery loss.
The EUROCLAUS concept
To meet the continuously increasing requirements for sulfur
recovery efficiency (SRE), a new process should be capable of
meeting a SRE 99.5%, which complies with the highest European
standards (Germany, TA-Luft). It is expected that most of the
European countries will move towards this recovery level in the near
future.
This means that expected SREs should be between 99.6 - 99.7%, in
order to be able to guarantee 99.5%.

For obvious economic reasons, an adaptation of the modified Claus

process, being the world standard in sulfur recovery, would be the
preferred basis for a new process.
A minimum amount of catalytic stages should be involved,
preferably not more than three, as in the standard Claus process.
With two catalytic stages, high recovery levels cannot be achieved.
Four catalytic stages are less attractive with respect to investment
costs and increased pressure drop. Of course, low operating and
investment costs are of paramount importance for a successful new
process. The desirable process requirements are summarized in
Table 1.
The SUPERCLAUS process would be an excellent starting point to
meet these process requirements. The sulfur recovery efficiency
limitations of the process should, however, be overcome to meet the
required recovery efficiency of 99.5 SRE 99.9+%.
A convenient way to decrease SO 2 in the Claus tail gas would be by
reduction to S (and some H 2S) upstream of the selective H 2S
oxidation reactor. This process step should be simple and cost
effective.
Conversion of SO2 in the Claus tail gas, a decrease in H2S content in
the exit from R-2 Claus from 1.0 down to 0.80 vol%, and a
simultaneous increase in yield to sulfur from 85% to 90% in the
selective oxidation reactor would together result in a very large
increase of efficiency up to 99.5%.
The concept of reduction of SO 2 prior to selective oxidation of H 2S is
the basis of the EUROCLAUS process.
The process
The

new

EUROCLAUS

process, based

on

Claus

chemistry,

hydrogenation of SO2 and selective oxidation of H2S, is an acronym

for Extremely Upgraded Reduction Oxidation CLAUS'.

Figure 3 shows an overview of the new process. The front end is

composed of the well known Claus process, consisting of a thermal
stage and a first catalytic Claus stage. In the second catalytic
reactor, a top layer of normal Claus catalyst is positioned above a
layer of another type of catalyst with hydrogenating properties for
conversion of SO2 to S and H2S. The last stage is the well known
selective oxidation stage as applied in the SUPERCLAUS
process.
In the EUROCLAUS process, sulfur is produced along three
different pathways.
Claus reaction
In the Claus section, which also includes the Claus catalyst in the
top part of the last Claus reactor, sulfur is made according to the
well known Claus reaction:
2 H2S + SO2 3/n Sn + 2 H2O

(3)

Catalytic reduction of SO2

SO2 is reduced to sulfur vapor and H 2S in the reduction stage, where
H2 and CO have already been present in the Claus process gas
reacts with SO2 according to:
SO2 + 2 H2 1 /n Sn + 2 H2O
SO2 + 3 H2 H2S + 2 H2O
SO2 + 2 CO 1 /n Sn + 2 CO2

(4)
(5)
(6)

Selective oxidation of H2S

Finally, H2S is oxidized with a high sulfur yield, avoiding the
limitations of the Claus equilibrium, to sulfur vapor in the selective
oxidation stage according to:

H2S + 0.5 O2 1 /n Sn + H2O

(1)

In this way, a much improved sulfur recovery efficiency is made

possible by:

Bulk removal of sulfur in the Claus section.

Selective hydrogenation of the remaining SO2.

Oxidation of H2S to sulfur.

Catalyst
The catalytic reduction of SO2 is performed over a sulfur resistant
catalyst. Normal Claus process gas contains sufficient H 2 and CO for
the catalytic reduction of small amounts of SO2.
Loss of sulfur and production of SO 2/COS may occur as a result of
the following side reactions during the catalytic hydrogenation:
reverse Claus reaction:
3/n Sn + 2 H2O 2 H2S + SO2

(2)

reduction of sulfur vapour in the feed:

1/n Sn + H2 H2S

(7)

formation of COS:
1 /n Sn + CO COS

(8)

H2S + CO COS + H2
SO2 + 3CO COS + 2CO2

(9)
(10)

The choice of hydrogenation catalyst and process conditions should

be such that the above reactions are minimized. The type of catalyst
and optimum operating conditions have been determined in
laboratory tests, for a process configuration with a thin layer of
reduction catalyst in the bottom section of the second catalytic
Claus reactor, preceding the selective oxidation stage. The reduction
capabilities under proper operating conditions, using an optimized
catalyst, are shown in Table 2.

The laboratory data in Table 2 show that bulk SO 2 conversion is

achieved. Even with a high content of sulfur vapor and CO in the
process gas, a high selectivity towards sulfur is measured. No
reduction of sulfur vapor in the feed occurs.
Better performance of selective oxidation reactor
It has been experienced and confirmed by considerable laboratory
test data, with different types of selective oxidation catalyst, that
the yield to sulfur in the oxidation reactor is a function of the
catalyst bed bottom temperature. In case of too low a temperature,
the last 5 - 10% of the incoming H 2S is not converted to sulfur and a
larger

slippage

of

H2S

is

experienced.

Too

high

bottom

temperature will result in more SO2 formation by catalytic and gas

phase oxidation of H2S and sulfur vapor.
For the second generation type of selective oxidation catalyst, the
catalyst bed bottom temperature should be maintained below
approximately 260 C for a maximum sulfur yield.
A typical sulfur yield measured in plants is 86 - 91%. Newly
developed selective oxidation catalysts reach 94 96% yields in a
laboratory reactor. This indicates that further yield improvements for
large commercial reactors may be achievable.
A selective oxidation reactor inlet temperature of 205 - 215 C is
normally used. Therefore, the acceptable delta-T in the selective
oxidation reactor is limited to 50 C for maximum yield.
The exothermic heat of reaction from oxidation of H 2S to sulfur
vapor (and some SO2) results in a temperature rise of approximately
70 C per 1 vol% H2S. Therefore, the H2S inlet concentration is
limited to approximately 0.7 vol% H2S to maintain a maximum yield.
This corresponds to an H2S outlet concentration from the second
Claus reactor stage of approximately 0.8 vol%, because of dilution
by the inline burner reheater flue gas and/or selective oxidation air
upstream of the oxidation reactor.

For this reason, the EUROCLAUS process configuration, with a

decreased H2S content of 0.8 vol% in the outlet of the last catalytic
Claus stage, fits better in the optimum operating window of the
selective oxidation reactor. This will result in a higher sulfur yield.
Figure 4 shows the temperature profile ; through the catalyst bed at
a high inlet temperature (curve 1) and at a low inlet temperature
(curve 2). Curve 1 gives too much SO 2 production in the reactor
bottom, whereas curve 2 gives too much H2S slippage. An optimum
inlet temperature is important for a high sulfur yield.
The third development is an improved control system of the
selective oxidation stage. The flow of selective oxidation air is
determined by the plant capacity, the H 2S content in the process
gas to the selective oxidation reactor, and the oxygen concentration
in the process gas from the selective oxidation stage.
The correlation between these variables:
Selective Oxidation Air Flow = f (plant capacity, H 2S in, O2 out)
provides a tool to maintain an optimum oxygen concentration in the
reactor outlet process gas. This will also result in a higher sulfur
yield.
A comparison of sulfur recovery efficiencies of:

A conventional modified Claus unit with three catalytic reactor

stages.

A SUPERCLAUS unit with two Claus reactors and one

selective oxidation reactor.

An EUROCLAUS unit with three reactors.

is presented in Figure 5. Very high recovery efficiencies of 99.5% can

be reached with EUROCLAUS.

A further improvement of the SRE may be achieved with a so-called

'deep cooler'. This vertically positioned heat exchanger is cooled
with ambient air and is positioned downstream of the final sulfur
condenser.

The

deep

cooler

cools

the

process

gas

to

the

solidification temperature of sulfur, which is 114.5 C. Thus, the

sulfur vapor losses are now reduced to very low values. The deep
cooler, which operates continuously without being plugged with
solid sulfur, may add another 0.1 - 0.2% recovery efficiency.
Utility consumption
The SUPERCLAUS and EUROCLAUS processes have low utility
consumptions. In Table 3, the utility consumptions have been
compared with the standard Claus process on the basis of a 100 tpd
three stage Claus plant, with a feed gas containing 90% H 2S and
catalytic incineration of the offgases.
Conclusion
The

EUROCLAUS

conventional

Claus

process
process

increases

sulfur

significantly

recovery

and

of

the

involves

the

introduction of selective reduction of SO 2 followed by selective

oxidation of H2S directly into sulfur in the last reactor stage. Sulfur
recoveries of 99 - 99.7% are achievable, depending on feed gas
composition.
EUROCLAUS is a fundamental improvement of SUPERCLAUS,
making the process suitable for the 21s' century (patents are filed).
The calculated recovery efficiencies are shown in Figure 6. The
recovery

efficiencies

are

based

on

high

COS/CS 2

hydrolysis

efficiencies (95%) in the first Claus reactor and a tail gas

temperature of 125 C. Already five commercial units are being

designed.

Figure 1- The Claus process

Figure 2 The SUPERCLAUS process

Figure 3 The EUROCLAUS process

Figure 4 Temperature profiles in selective oxidation reactor

Figure 5 Performance of sulfur plants

Figure 6. EUROCLAUS capabilities

Table 1 Process requirements of enhanced SRU

Table 2 Reduction of SO2

Table 3 -