TUD-1 type aluminosilicate acid catalysts for 1-butene oligomerisation


TUD-1 type mesoporous aluminosilicates were explored for the acid-catalysed oligomerisation of 1-butene, under high pressure, continuous flow operation, which is an attractive route to produce sulphur-free synthetic fuels with reduced aromatics content. The solid acid catalysts were synthesised via one-pot synthesis (HT) or stepwise approach (PG), without using surfactants as templates, which is an eco-friendly characteristic of the TUD-1 family. While the HT approach may be advantageous in terms of process intensification in relation to the PG one, the latter may lead to relatively low molar ratios Si/Al. The catalysts possessed Si/Al ratios in the range 3-5 and 17-35 for the PG and HT approaches, respectively, pore sizes in the range 10-14 nm, and essentially Lewis acidity. To the best of our knowledge, this is the first report of siliceous oxide TUD-1 furnished with acidity via post-synthesis grafting (PG) of Al-species. For comparative studies, an ordered mesoporous aluminosilicate was synthesised via the PG approach using surfactant mixtures. All materials prepared promoted the reaction of 1-butene to higher molar mass products. The best-performing catalyst in terms of space-time yields of the 170-390 degrees C cut (boiling point range) products (of the type middle distillates) was Al-TUD-1(25)-HT synthesised via the HT method. The products were analysed by comprehensive two-dimensional gas chromatography (GC xGC) combined with time-of-flight mass spectrometry (ToFMS). The influence of material properties and process parameters on the catalytic reaction, and catalyst stability were studied. The catalytic performances were benchmarked with ZSM-5 (zeolite used in commercial oligomerisation processes).



subject category

Energy & Fuels; Engineering


Silva, AF; Fernandes, A; Antunes, MM; Neves, P; Rocha, SM; Ribeiro, MF; Pillinger, M; Ribeiro, J; Silva, CM; Valente, AA

our authors


This work was developed in the scope of the project (Associate Laboratory) CICECO Aveiro Institute of Materials-POCI-01-0145-FEDER-007679 [FCT (Fundacao para a Ciencia e a Tecnologia) ref. UID/CTM/50011/2013], and QOPNA research Unit (FCT UID/QUI/00062/2013), financed by national funds through the FCT/MEC and when applicable co-financed by FEDER (Fundo Europeu de Desenvolvimento Regional) under the PT2020 Partnership Agreement. The FCT and the European Union are acknowledged for a Ph. D. grant to A.F.S. (SFRH/BD/101018/2014)), and post-doctoral grants to M.A. (SFRH/BPD/89068/2012) and P.N. (SFRH/BPD/110530/2015), cofunded by MCTES and the European Social Fund through the program POPH of QREN. The authors wish to thank Saint-Gobain Ceramic Materials AS for generously supplying the SIKA SiC sample.

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