abstract
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).
keywords
ZEOLITE-BASED CATALYST; QUALITY LIQUID FUELS; FISCHER-TROPSCH; DIESEL FUELS; MESOPOROUS ALUMINOSILICATES; OLEFINS OLIGOMERIZATION; TRANSPORTATION FUELS; CONVERSION; SELECTIVITY; ISOBUTENE
subject category
Energy & Fuels; Engineering
authors
Silva, AF; Fernandes, A; Antunes, MM; Neves, P; Rocha, SM; Ribeiro, MF; Pillinger, M; Ribeiro, J; Silva, CM; Valente, AA
our authors
Anabela Tavares Aguiar Valente
Principal Researcher
Andreia de Freitas Silva
Research Fellowship
Carlos Manuel Silva
Associate Professor
Maria Margarida Feitor Pintão Moreno Antunes
Junior Researcher
Martyn Pillinger
Principal Researcher
Patrícia dos Santos Neves
Assistant Researcheracknowledgements
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.