MINDTHEGAP

Lorena Oviol, Manuel Bruns, Vladimir Fridman, Jay Merriam and Michael Urbancic, Sd-Chemie, a Clariant Group Company, take a look at the next generation in onpurpose olefins production.

he rapid emergence of shale gas has fundamentally shifted the balance in the olens markets. As natural gas prices drop with increasing supply, olen cracker operators have shifted to lighter feed and are therefore producing lower levels of propylene and higher olens. When added to new light cracker production from the Middle East, the gap between supply of C3, C4 and higher olens compared to the growing demand of their derivatives continues to expand. These market trends have combined to create a urry of interest in the so called on purpose olens production technologies.

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The Houdry process for olen production is one of the earliest petrochemical technologies. It was developed by Eugene Houdry in 1942 to remove hydrogen from parafns 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 Caton technologies. Since acquiring the Houdry processes more than 20 years ago, Sd-Chemie has continued to improve the Catadiene and Caton catalysts by working with its exclusive licensing partner, Lummus Technology, a CB&I business sector. The recent improvements made to the Caton and Catadiene catalysts and processes have helped to boost their competitiveness and reliability for dehydrogenation processes.

Catalyst improvements
The Caton and Catadiene processes are xed bed, cyclic processes in which light parafns are catalytically dehydrogenated to produce the corresponding olens and

Figure 1. Cyclic operation of a Catofin and

Catadiene dehydrogenation reactor.

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 ow 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 ow 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 rst 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 -chromium oxide and -aluminum oxide or -(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 conrm the improved performance (Table 1). The previous generation catalyst, Caton STD, was tested after 637 days on stream (DOS) of commercial operation in a propane dehydrogenation plant, and compared to the next generation Caton 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 signicantly less formation of -(Cr, Al)2O3, which explains the higher observed activity and selectivity retention.

Equipment reliability improvement

The Caton 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 reected in the >98% on stream factor that is typical for operating units. Specic 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
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Figure 2. Propane conversion over Catofin PS

catalyst with and without HGM at the same pilot plant conditions.

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dehydrogenation units in commercial operation are using Caton 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 Caton unit on the Texas Gulf Coast, USA, slated for start up in 2015.

(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 Me + O2 MeOx H < 0 H < 0 (1) (2)

Next generation technology

Heat input to the catalyst bed has been a critical limiting factor for these dehydrogenation processes, restricting parafn conversion and therefore the olen production rate. This was mainly the result of air ow 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.

Upon loading in the catalyst bed, HGM has direct contact with the catalyst. This enhances heat transfer efciency and allows optimisation of the catalyst bed temperature prole for the subsequent endothermic dehydrogenation reaction. This approach considerably reduces the heat limitations of the original process. The rst experiments to test the HGM concept in an adiabatic pilot plant were very encouraging, and conrmed that addition of HGM to the catalyst bed allowed the same parafn conversion to be achieved at signicantly lower air inlet temperatures, or much higher parafn 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 prole in the dehydrogenation catalyst bed, eliminating exposure of the product olen to the higher temperatures, which can cause byproduct formation, and thereby improving the propylene selectivity. Alternatively, HGM can provide an optimal conversion prole in the catalyst bed that minimises the retention time of the product olen. These factors combine to promote an increase in total propylene selectivity and thus increase the yield of the Caton process. Extensive additional tests conrm 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 Days on stream -(Cr,Al)2O3 [wt%] Propane conversion* 637 56 23% 80%

Catofin PS 991 29 80% 100%

Figure 4. HGM can give a significant boost in

Propylene selectivity* *Relative to fresh base catalyst

selectivity over catalyst systems without HGM.

Reprinted from September 2012

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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 benets have been incorporated into the latest Caton propane dehydrogenation plant design.

lower energy consumption, continuing the high performance of these catalysts.

Notes
Houdry, Caton and Catadiene are registered trademarks of Sd-Chemie, Inc.

References
1. 2. 3. 4. 5. 6.

Commercial demonstration
The actual performance of HGM compared to a non-HGM case in the rst 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 conguration and comparable severity. Thus improved selectivity for the HGM case has been conrmed in commercial operations.

7.

8. 9.

Conclusion
Ongoing research and technical service efforts in the catalyst and process technology for Caton and Catadiene have resulted in improved performance for propylene, isobutylene and butadiene producers. The most recent technology breakthrough, the proprietary HGM, can signicantly boost selectivity and

10. 11.

HORNADAY, G.F., Petroleum Refiner, Vol. 6, N4, September (1953). HOUDRY, E.J. US Patent 2,423,029 (1947). HOUDRY, E.J. US Patent 2,419,997 (1947). BEESLEY, E.; WIPP, B.,'Butane Dehydrogenation at Billingham' Chem & Ind. (London), 1953, S50 (Aug 2010). HORNADAY, G.F.; FERRELL F.M., Advances in Petroleum Chemistry and Refining, Vol.4, Interscience, Paris, 1961, pp451488. 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. 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. 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. 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. FRIDMAN, V.Z.; MERRIAM, J.; URBANCIC, M. 'Catalytically inactive heat generator and improved dehydrogenation process', US Patent No. 7,622,623 (2009). FRIDMAN, V.Z. URBANCIC, M. 'Endothermic hydrocarbon conversion process', US Patent No. 7,973,207 (2011).

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