1-Butene oligomerization over ZSM-5 zeolite: Part 1 – Effect of reaction conditions A. Coelho a , G. Caeiro b , M.A.N.D.A. Lemos a,⇑ , F. Lemos a , F. Ramôa Ribeiro a a IBB – Institute for Biotechnology and Bioengineering, Centre for Biological and Chemical Engineering, Instituto Superior Técnico, UTL, Av. Rovisco Pais, 1049-001 Lisboa, Portugal b Galp Energia, SGPS, S.A., Rua Tomás da Fonseca, 1600-209 Lisboa, Portugal highlights  Systematic study of the conversion of 1-butene into fuels by oligomerization over HZSM-5 catalysts.  Optimum conditions for selectivity for C þ 8 hydrocarbons (86 wt.%) was obtained with H-ZSM-5, at 200 °C and 0.5 bar.  HZSM-5 is a suitable catalyst and allows almost steady-state operation.  Deactivation, with consequent decrease in acidity, improves the performance of the catalyst under some conditions.  Low temperature performance of the catalyst seems to be hindered by the volatility of the products. graphical abstract article info Article history: Received 7 June 2012 Received in revised form 24 March 2013 Accepted 25 March 2013 Available online 9 April 2013 Keywords: 1-Butene oligomerization H-ZSM-5 zeolite Catalyst deactivation Heterogeneous catalysis Light olefins abstract The demand for middle distillates (kerosene and diesel) in comparison to gasoline fractions is increasing constantly, particularly in the majority of European countries. Thus, maximizing the production of middle distillates in the refining process is of immediate interest to refiners. However, the production of liquid fuels, for instances using a catalytic cracker, always generates a significant amount of lighter fractions, in particular of olefinic nature. Thus, the use of oligomerization reactions to convert the lighter olefin cuts into middle distillates to incorporate in the diesel pool is a promising process for the production of clean diesel fractions. In this work, 1-butene oligomerization over H-ZSM-5 zeolite has been investigated in a differential reactor operating at ambient pressure. The effect of the reaction conditions, such as reaction temperature, contact time and partial pressure was studied on the activity, selectivity and stability of the catalyst. The results show that an increase in the reaction temperature and/or partial pressure and in the contact time produces an improved catalyst activity. The data also show that high partial pressure improves the selectivity to C þ 8 . Moreover, when increasing the temperature from 150 °C to 200 °C the C þ 8 hydrocarbons selectivity increases, whereas above this temperature it decreases as expected, due to the competition of cracking reactions. Furthermore, a decrease in contact time between the reaction mix- ture and the acid sites of the catalyst caused the C þ 8 hydrocarbons fraction in the product to increase. The highest selectivity towards C þ 8 hydrocarbons (86 wt.%) was obtained with H-ZSM-5, at 200 °C and 50 kPa of partial pressure and for the lowest value of contact time analyzed (12.5  10 3 h). In this way, the operating conditions must be tuned in order to achieve a significant conversion and selectivity in desired fraction (C þ 8 ). Ó 2013 Elsevier Ltd. All rights reserved. 0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.fuel.2013.03.066 ⇑ Corresponding author. Tel.: +351 21 841 78 90; fax: +351 21 841 91 98. E-mail address: mandal@ist.utl.pt (M.A.N.D.A. Lemos). Fuel 111 (2013) 449–460 Contents lists available at SciVerse ScienceDirect Fuel journal homepage: www.elsevier.com/locate/fuel