MINDTHEGAP

Lorena Oviol, Manuel Bruns, Vladimir Fridman, Jay Merriam and

Michael Urbancic, Süd-Chemie, a Clariant Group Company, take
a look at the next generation in on purpose olefins production.

T
he rapid emergence of shale gas has fundamentally
shifted the balance in the olefins markets. As natural gas
prices drop with increasing supply, olefin cracker
operators have shifted to lighter feed and are therefore
producing lower levels of propylene and higher olefins. When added
to new light cracker production from the Middle East, the gap
between supply of C3, C4 and higher olefins compared to the growing
demand of their derivatives continues to expand. These market
trends have combined to create a flurry of interest in the so called
‘on purpose’ olefins production technologies.

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Catalysis & energy
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 The Houdry® process for olefin production is one of the
earliest petrochemical technologies. It was developed by
Eugene Houdry in 1942 to remove hydrogen from paraffins with
high conversion and selectivity. This process was initially used
for production of butylenes during World War Two. Later,
Houdry further developed and commercialised the process for
one stage dehydrogenation of n-butane into butadiene in what
is now known as the Catadiene® process.1 Later, in the 1980s, this
technology was applied to the production of isobutylene for
methyl tertiary butyl ether (MTBE) by dehydrogenation of
isobutane. In the 1990s, it was utilised for production of
propylene by dehydrogenation of propane. These processes are
known as the Catofin® technologies.
Since acquiring the Houdry processes more than 20 years
ago, Süd-Chemie has continued to improve the Catadiene and
Catofin catalysts by working with its exclusive licensing partner,
Lummus Technology, a CB&I business sector. The recent
improvements made to the Catofin and Catadiene catalysts and
processes have helped to boost their competitiveness and
reliability for dehydrogenation processes.
Catalyst improvements
The Catofin and Catadiene processes are fixed bed, cyclic
processes in which light paraffins are catalytically
dehydrogenated to produce the corresponding olefins and
Figure 1. Cyclic operation of a Catofin and
Catadiene dehydrogenation reactor.
Figure 2. Propane conversion over Catofin PS
catalyst with and without HGM at the same pilot
plant conditions.
hydrogen. These processes are designed to run adiabatically,
with the catalyst on hydrocarbon feed for very short cycles
(7 – 15 mins), followed by regeneration of the catalyst for a
similar period of time.2, 3 The key principal of the process is that
the consumption of heat during the endothermic
dehydrogenation reaction is closely in balance with the heat
restored to the bed during the reheat cycle. Hot air flow and
combustion of coke are two main sources of heat input to the
bed.
During operation, the reactor vessel cycles between the
dehydrogenation step and the regeneration step. Multiple
reactors are used to maintain a continuous product flow with a
typical cycle length of 20 – 30 mins. The cyclic nature of these
processes is illustrated graphically in Figure 1.
High activity, high selectivity and long catalyst life are key
performance demands for the cost effective production of
propylene, isobutylene and butadiene. The thermodynamics of
dehydrogenation require operation at a relatively high
temperature (600 – 650 ˚C), thus demanding a robust catalyst.
Under these harsh operating conditions, the first generation
proprietary chromium oxide/alumina catalysts had a lifetime of
only six months.4, 5
After extensive study, the primary cause of catalyst
deactivation was shown to be the conversion of the active
chromium oxide phase into an inactive solid solution of
α-chromium oxide and α-aluminum oxide or α-(Cr, Al)2O3
phase.6 – 9 This understanding led to the development of more
stable catalysts in which the migration of chromium into the
alumina lattice is inhibited. The latest generation catalysts
show high performance for periods spanning approximately
3 – 4 years.
The results from performance testing of spent catalysts
confirm the improved performance (Table 1). The previous
generation catalyst, Catofin STD, was tested after 637 days on
stream (DOS) of commercial operation in a propane
dehydrogenation plant, and compared to the next generation
Catofin PS catalyst. Even after 50% longer service, the PS version
still exhibits much greater conversion and selectivity compared
to the previous catalyst.
The data also shows that despite having a much longer on
stream time, the latest generation catalyst had significantly less
formation of α-(Cr, Al)2O3, which explains the higher observed
activity and selectivity retention.
Equipment reliability
improvement
The Catofin and Catadiene technologies have long operating
histories for propylene, isobutylene and butadiene production.
The experience gained through years of operation has been
implemented to boost the catalyst performance, and to
improve the design of major equipment to increase the unit
reliability. The value of this ongoing development is reflected in
the >98% on stream factor that is typical for operating units.
Specific improvements made in recent years include:
integrated equipment to optimise heat balance, maximum use
of exhaust streams for better energy savings and improved valve
construction for even greater reliability.
This experience has also applied to the scale up of this
technology, and unit capacities of up to 850 000 metric tpy are
now possible. Currently the three largest propane
HYDROCARBON
ENGINEERING Reprinted from September 2012
 dehydrogenation units in commercial operation are using
Catofin technology:
nn Petrologistics, Texas, USA.
nn Advanced Petrochemical Company, Jubail Industrial City,
Kingdom of Saudi Arabia.
nn Saudi Polyolefins Co., Jubail Industrial City, Kingdom of
Saudi Arabia.
Furthermore, Enterprise Products Partners have recently
announced that they will build a new 750 000 metric tpy
Catofin unit on the Texas Gulf Coast, USA, slated for start up in
2015.
Next generation technology
Heat input to the catalyst bed has been a critical limiting factor
for these dehydrogenation processes, restricting paraffin
conversion and therefore the olefin production rate. This was
mainly the result of air flow rate limitations due to pressure
drop across the bed, and the short regeneration time. To address
this issue, a novel approach to heat transfer to the bed had to
be developed, one that could take advantage of the fact that
this process operates in a cyclic, reduction oxidation mode.
After several years of investigation, a new material was
developed that is referred to as ‘heat generating material’
Figure 3. Propylene selectivity as a function of
propane conversion over Catofin PS catalyst, with
and without HGM.
Figure 4. HGM can give a significant boost in
selectivity over catalyst systems without HGM.
HYDROCARBON
Reprinted from September 2012 ENGINEERING
(HGM).10, 11 This material meets several key performance
parameters, including the ability to produce heat while
remaining inactive to the feed and products; and shows no
negative impact on the activity, selectivity or lifetime of the
catalyst.
The HGM product consists of a metal oxide on a
proprietary support that chemically generates heat in situ.
During the reduction stage of the cycle, the metal oxide is
reduced with the generation of heat (Equation 1). During the
regeneration stage of the cycle, the reduced metal is converted
back to the oxide form providing an additional amount of heat
(Equation 2):
MeOx + H2  Me + H2O ΔH < 0 (1)
Me + O2  MeOx ΔH < 0 (2)
Upon loading in the catalyst bed, HGM has direct contact
with the catalyst. This enhances heat transfer efficiency and
allows optimisation of the catalyst bed temperature profile for
the subsequent endothermic dehydrogenation reaction. This
approach considerably reduces the heat limitations of the
original process.
The first experiments to test the HGM concept in an
adiabatic pilot plant were very encouraging, and confirmed that
addition of HGM to the catalyst bed allowed the same paraffin
conversion to be achieved at significantly lower air inlet
temperatures, or much higher paraffin conversion at the same
air temperature (Figure 2).
Operation at lower air temperature can reduce the
deactivation rate of the catalyst and thus provide longer catalyst
life. Perhaps more interestingly, a dramatic increase in propylene
selectivity was also observed with the use of HGM (Figure 3).
Of course, HGM does not change the intrinsic selectivity of
the catalyst. However, by proper design HGM can provide the
optimum temperature profile in the dehydrogenation catalyst
bed, eliminating exposure of the product olefin to the higher
temperatures, which can cause byproduct formation, and
thereby improving the propylene selectivity. Alternatively, HGM
can provide an optimal conversion profile in the catalyst bed
that minimises the retention time of the product olefin. These
factors combine to promote an increase in total propylene
selectivity and thus increase the yield of the Catofin process.
Extensive additional tests confirm that the application of
this concept will allow:
nn A significant increase of the olefin production rate by
increasing the yield or by operation at higher liquid hourly
space velocity (LHSV).
Table 1. Properties of catalyst samples taken from the
same commercial plant show the improvement in
stability of the latest generation catalyst
Catofin STD Catofin PS
Days on stream 637 991
α-(Cr,Al)2O3 [wt%] 56 29
Propane conversion* 23% 80%
Propylene selectivity* 80% 100%
*Relative to fresh base catalyst
 nn A significant increase of the olefin selectivity and reduction
of the monomer factor by optimising the catalyst bed
temperature profile.
nn Lower energy consumption by reducing the amount of air
used during the regeneration part of the cycle without
reducing the production rate.
nn Further reduction in the inlet hydrocarbon temperature to
further increase olefin selectivity.
nn Increase catalyst life by minimising the air inlet temperature.
nn An increase in the number of reactors that are operating in
the dehydrogenation mode at the same time.
The majority of these benefits have been incorporated into
the latest Catofin propane dehydrogenation plant design.
Commercial demonstration
The actual performance of HGM compared to a non-HGM case
in the first commercial operation is shown in Figure 4. Note that
the data for conversion and selectivity of the processes is
compared at equivalent operating conditions using the same
catalyst loading configuration and comparable severity. Thus
improved selectivity for the HGM case has been confirmed in
commercial operations.
Conclusion
Ongoing research and technical service efforts in the catalyst
and process technology for Catofin and Catadiene have resulted
in improved performance for propylene, isobutylene and
butadiene producers. The most recent technology breakthrough,
the proprietary HGM, can significantly boost selectivity and
Clariant international ltd
Rothausstrasse 61
4132 Muttenz
Switzerland
Catalysis & energy
catalyst@clariant.com
www.Catalysis-energy.Clariant.Com
lower energy consumption, continuing the high performance of
these catalysts.
Notes
Houdry, Catofin and Catadiene are registered trademarks of
Süd-Chemie, Inc.
References
1. HORNADAY, G.F., Petroleum Refiner, Vol. 6, N4, September (1953).
2. HOUDRY, E.J. US Patent 2,423,029 (1947).
3. HOUDRY, E.J. US Patent 2,419,997 (1947).
4. BEESLEY, E.; WIPP, B.,'Butane Dehydrogenation at Billingham' Chem
& Ind. (London), 1953, S50 (Aug 2010).
5. HORNADAY, G.F.; FERRELL F.M., Advances in Petroleum
Chemistry and Refining, Vol.4, Interscience, Paris, 1961,
6.
pp 451 – 488.
ROKICKI, A; BRUMMER, R; FRIDMAN, V.Z. 'Catalyst and
process improvements for increased stability CATOFIN i-C4
and C3 dehydrogenation'. Catalysts in Petroleum Refining and
Petrochemicals, Proceeding of Saudi-Japanese Symposium, 11th,
Dhahran, Saudi Arabia, Nov. 11 – 12, 2001.
7. URBANCIC, M.A.; FRIDMAN, V.Z.; ROKICKI, A. 'A New Houdry
Catalyst for the ‘Third wave’ - Propane Dehydrogenation',
Proceedings of 19th North American Catalysis Society Meeting,
Philadelphia, 2005.
8. FRIDMAN, V.Z.; ROMAINE-SCHMIDT, E. 'Reduction of the Al-Cr
catalyst selectivity as a result of its deactivation', Proceedings 21st
North American Catalysis Society Meeting, San Francisco, 2009.
9. FRIDMAN, V.Z.; DAVIES, S.; HOWARD, J.; JASINSKI J. 'Stability
of active sites precursors of Al-Cr dehydrogenation catalyst',
Proceedings 22nd North American Catalysis Society Meeting, Detroit,
2011.
10. FRIDMAN, V.Z.; MERRIAM, J.; URBANCIC, M. 'Catalytically inactive
heat generator and improved dehydrogenation process', US Patent
No. 7,622,623 (2009).
11. FRIDMAN, V.Z. URBANCIC, M. 'Endothermic hydrocarbon conversion
process', US Patent No. 7,973,207 (2011).
HYDROCARBON
ENGINEERING Reprinted from September 2012