Olefins via catalytic partial oxidation of light alkanes over Pt/LaMnO 3 monoliths L. Basini a , S. Cimino b,⇑ , A. Guarinoni a , G. Russo b , V. Arca c a eni, Refining & Marketing Division, Italy b Istituto Ricerche sulla Combustione CNR, Italy c eni Versalis S.p.A., Italy highlights " CPO of ethane and n-butane to olefins was studied on Pt–Sn/LaMnO 3 honeycombs. " Bench scale testing showed high single pass yields of C 2 H 4 +C 3 H 6 around 55 wt.%. " Stable reactivity demonstrated for 500 h.o.s. with ethane feed and sacrificial H 2 . " Pt–Sn/LaMnO 3 catalyst guaranteed a net hydrogen production across CPO reactor. " Products quenching & catalyst overheating issues were identified during scale-up. article info Article history: Available online xxxx Keywords: Olefins production Catalytic partial oxidation Light alkanes Pt perovskite Structured catalyst Long-term stability abstract The reactivity of a multi-layered monolith catalyst containing Pt and Sn over LaMnO 3 /La-c-Al 2 O 3 /cordi- erite, previously studied in a lab-scale plant for producing ethylene via Short Contact Time – Catalytic Partial Oxidation of ethane, has been further and extensively investigated in a bench-scale plant with higher production capacity. Ethylene yields exceeding 55 wt.% have been achieved and the reactivity per- formances have been maintained for more than 500 h.o.s. The experiments, while confirming the poten- tial of the technology, have pointed out some weakness in catalyst stability and reactor design. The bench-scale experimental study has also addressed the reactivity features of n-butane indicating that ethylene + propylene yields approach 54 wt.% in a wide range of experimental conditions. Ó 2012 Elsevier B.V. All rights reserved. 1. Introduction Light olefins are the most important building blocks for the polymers and variety of intermediates industry. World demand of ethylene and propylene is exceeding now 180 MTA (about 2/3 related to ethylene production), with an annual growth of 4–5% in the next decade [1,2]. Steam cracking of hydrocarbons has been and still is the main industrial technology for producing light olefins [1–4]. However, despite the technological improvements occurred in more than 50 years, steam cracking remains the most energy-consuming pro- cess in the petrochemical industry. It is expected that the possibility to perform oxidative dehydro- genation (ODH) or oxy-cracking of light alkanes through Short Contact Time – Catalytic Partial Oxidation (SCT–CPO) would lead to a novel technology with low capital investment, improved energy efficiency [2–6] and reduced NO x and CO 2 emissions. In par- ticular, it has been shown that monolithic Pt-based catalysts, oper- ated under autothermal conditions – i.e. wherein the feed is partially combusted to drive the endothermic cracking process- can efficiently convert ethane to ethylene, propane and n-butane to ethylene and propylene, isobutane to propylene, isobutene and ethylene [3–20]. Recent experiments performed at laboratory scale utilizing eth- ane and a patented Pt(–Sn)/LaMnO 3 catalysts [10,11], have pro- duced olefins with yields exceeding 61 wt.% and selectivity above 75 wt.% per pass. It has been estimated that these reactivity fea- tures could result in reduced production cost of ethylene with re- spect to steam cracking [10]. Indeed the advantages resulting from the high olefin yields and the compact reactor system [4–6,9] could more than compensate the additional oxygen consumption costs, not to mention the benefit of reducing the CO 2 and NO x emissions by avoiding large heating furnaces. However, from a technical standpoint, a better definition of sev- eral key operating issues is required, including: catalyst activity and stability as well as reactor design [5,8,9,12,13,16]. In fact, most of the available experimental results were obtained with small 1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cej.2012.06.153 ⇑ Corresponding author. Address: Istituto Ricerche sulla Combustione CNR, P.le V. Tecchio 80, 80125 Napoli, Italy. Tel.: +39 081 7682233; fax: +39 081 5936936. E-mail address: stefano.cimino@cnr.it (S. Cimino). Chemical Engineering Journal xxx (2012) xxx–xxx Contents lists available at SciVerse ScienceDirect Chemical Engineering Journal journal homepage: www.elsevier.com/locate/cej Please cite this article in press as: L. Basini et al., Olefins via catalytic partial oxidation of light alkanes over Pt/LaMnO 3 monoliths, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.06.153