Engelhard DD-931:

Titania alumina spheres for Claus catalysts

A Technology Update

Engelhard DD-931 titania-based Claus catalyst

Spherical titania-alumina catalyst
High CS
2
and COS conversions
Excellent price / performance value
Higher macroporosity, stronger and more durable than pure titania extrudates
Outperforms pure titania when converter feeds contains BTX
Allows customized loading
Over 20 units installed worldwide


Use of catalysts in the Claus process

Activated alumina and titania have been known and used for many years as Claus plant
catalyst. Engelhard DD-431 is recognized as the leading activated alumina catalyst
worldwide and SRC 99ti is the Engelhard titania catalyst.

Alumina catalysts are normally very efficient at converting H
2
S / SO
2
to sulfur.
However, alumina catalysts are generally not capable of achieving the high level of
conversion of carbon sulfide compounds often required for high overall sulfur recovery.
Titania catalysts can do this well, however, they are expensive, and the extrudates are
more fragile than spheres.


A new generation of promoted catalysts

Engelhard has now taken the development of Claus catalysts one step further by
combining the best features of both types of catalyst into a revolutionary product called
DD-931. This is a titania alumina composite containing substantial amounts of titania.
It is a 4 mm sphere, which makes it easy to handle. It has a high surface area
compared to titania extrudates.

Engelhard DD-931 also contains reasonable macroporosity, yet has much better
strength properties than titania extrudates, with very little macroporosity. Since DD-931
does contain a substantial amount of titania, it has much improved activity for CS
2
and
COS decomposition compared to just activated alumina.

Introduced in early 2001, Engelhard DD-931 catalyst has been installed in over 20
commercial units around the world by mid-2004. It continues to work to provide
exceptional performance through improved operations at reduced costs.





1

Proven performance

Independent testing of Engelhard DD-931 catalyst was performed by Alberta Sulfur
Research Ltd., ARSL, in Calgary, Canada. Since all new catalysts are quite active, it is
normal to pre-age them before testing. Aging conditions were used to simulate a
catalyst that had been in operation for more than 3 years and exposed to oxygen and
sulfation.

The catalyst pretreatment and the activity test
conditions were identical to those used
previously for the evaluation of Engelhard
SRC 99ti and alumina, so that direct
comparison could be made.

The results for Engelhard DD-931, SRC 99ti
and alumina at 1000 GHSV are shown in
Figures 1 and 2.

For these aged catalysts, corresponding to
more than 3 years life, Figure 1 shows that
Engelhard DD-931 achieved CS
2

conversions above 80% at a temperature of
310C. This compares to 30% for alumina
and 96% for titania. Engelhard DD-931
achieved CS
2
conversions of over 90% at
temperatures approaching 320C.

The corresponding COS conversions are
shown in Figure 2. As expected, the COS
conversions were much higher than for the
CS
2
. Specifically, Engelhard DD-931
achieved over 95% COS decomposition even
at the lowest temperatures of 300C. This is significantly better than can be achieved
with alumina. It should be noted that the conversions of CS
2
and COS are being
measured under identical conditions for all the catalysts.

In commercial plants, some small variations may be observed depending upon
operating conditions, i.e. gas flow rate and gas composition. Specifically, improvement
in the CS
2
conversions over Engelhard DD-931 and alumina would be found if the
oxygen level is less than 300 ppm used for the test work at ASRL. Also if the H
2
S to
SO
2
ratio is higher than that used in the test, higher conversions could be achieved.
This means, that in practice, even higher CS
2
conversions could be anticipated for
Engelhard DD-931.





2

Additional CS
2
and COS decomposition data was generated at 2000 GHSV (see Figure
3). Under these conditions, Engelhard DD-931 achieved over 80% CS
2
conversion at
320C, compared to less than 20% for alumina. This is relevant because if only a half
bed of titania catalyst is used, the effective space velocity for the titania portion of the
catalyst bed increases to 2000 GHSV.

It is possible under a number of very
reasonable operating conditions to obtain very
high conversions of CS
2
with Engelhard DD-
931 titania composite catalyst. Experience has
shown that even high conversions than those
shown can be achieved at lower oxygen levels
and higher H
2
S / SO
2
ratios.


Effect of BTX on catalyst
performance

The origin of much of the CS
2
found in the feed to the #1 Claus converter is from a
mixture of benzene, toluene and xylene (BTX) in the incoming feed to the reaction
furnace. The concentration of BTX is particularly high in the feed to many Claus plants
associated with natural gas processing.

When BTX is combusted in the reaction furnace, it leads to CS
2
in the feed to the
catalyst reactors. If the BTX is not destroyed in the furnace then it carries through into
the catalyst beds where it cracks and fouls up the catalyst and causes rapid
deactivation of the catalyst furnace. Hence, the goal is to completely destroy all the
BTX in the furnace mainly by using high temperatures, but in practice this is not always
possible. In such cases, some BTX does get through to the catalyst and the rate of
deactivation of the catalyst becomes an important factor. Testing of the deactivation
caused by BTX was carried out at ASRL in conjunction with PetroCanada.

The test work at ASRL, contracted by PetroCanada, showed that carbon cracking
rapidly deactivates the pure titania catalyst, much faster than standard alumina catalyst.

Additional test work was arranged at ASRL to evaluate the performance of Engelhard
DD-931 titania composite catalyst under similar conditions. A simulated first converter
gas stream was made and 20,000 ppmv of benzene and 5,000 ppmv of toluene were
added.

A three day test was run during which the CS
2
conversion was measured. The CS
2

conversions started above 90% but then steadily declined, appearing to stabilize after 2
to 3 days.

3

At the end of this accelerated test with
very high concentrations of BTX, the
conversion of CS
2
with the composite
titania catalyst, Engelhard DD-931, was
higher than alumina, which in turn has
been reported to be significantly higher
than titania itself.

Results are shown in Figure 4. Further
work by ASRL has confirmed the
deactivation of pure titania catalyst
extrudates by BTX.

It is concluded that, for Claus feeds that still contain some BTX in the feed to the first
converter, Engelhard DD-931 has the potential to actually give higher CS
2
conversions
than either pure titania or alumina catalysts.


Conclusions

Engelhard DD-931 composite titania catalyst has been found to stand up well under
simulated aging. It also has the following advantages:

It is a 4 mm spherical catalyst. The spheres are stronger and more durable than
pure titania extrudates.

It is more economical than pure titania catalysts. Comparable performance can
be achieved through slightly higher temperatures or more than a bed.

For gas feeds which still contain BTX, it actually performs significantly better than pure
titania, which is prone to deactivate from cracking reactions.
















4

References

New Claus Catalyst Options for Higher Sulfur Recovery, M.J. Pearson, E.M. Mophett, P.D. Clark,
N.I. Dowling and M. Huang, Sulfur 2000, October 2000.

Quantifying the Effect of Individual Aromatic Contaminants on Claus Catalysts, P.P. Crevier, N.I.
Dowling, P.D. Clark and M. Huang, LRGCC, February 2001.

The Effect of Space Velocity and BTX on the Conversion of H
2
S / SO
2
and CS
2
over Titania
Catalysts, P.D. Clark, N.I. Dowling and M. Huang, 2004 Brimstone Sulfur Recovery Symposium,
September 2004.











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Printed in the U.S.A. 01/2006, EC-8621

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