Europacat XII, Kazan, 09/2015 The effect of dealumination with HCl on MFI and FER type zeolites on the dehydration of n-butanol D. Gunst 1,2, A. Verberckmoes 2 & M.-F. Reyniers Laboratorium for Chemical Technology (LCT), Ghent University, Department of Chemical Engineering and Technical Chemistry, Technologiepark Zwijnaarde Zwijnaarde Belgium 2 Industrial Catalysis and Adsorption Technology (INCAT), Ghent University, Department of Chemical Engineering and Technical Chemistry, Valentin Vaerwyckweg Ghent Belgium To decrease oil dependency many alternatives are being researched. A promising method is the dehydration of butanol to butenes with the use of zeolites. Products formed by this catalytic reaction can directly be used in polymer synthesis (cfr; iso-butene) or be further converted (on the same catlysts) by oligomerization and isomerization into higher carbon products. Acid leaching treatment: 0.1M HCl 1g catalyst / 100ml solution contact time 2 hr T = 100°C Intens washing NH 4 + exchange + calcination Introduction: Butanol dehydration as the link between the classic refinery and the bio refinery Scope: Acknowledgments: The evaluation of different zeolite catalysts and their acid treatments for the use of butanol dehydration to a range of butenes. Main aspects of the dehydration reaction were investigated: selectivity, activity and deactivation. The evaluation process takes all these effects in account to discuss the possibility to treat different zeolites with HCl to improve the dehydration of butanol to butenes. ZSM-11 Characteristics D.G. acknowledges a Dehousse grant from the University Ghent (FEA, Department IT&C) SampleSi/Al bulk Si/Al surface Conc brönsted (mmol/g) S Int (m²/g) S ext (m²/g) V Micro (cm³/g) V tot (cm³/g) MFI MFI_AT FER FER_AT Selectivity Deactivation Trans-buteneCis-butene N-buteneN-dibutylether MFI Conclusion High Throughput setup II: Ugent (LCT) P tot = 5 bar P BuOH,0 = 28.8 kPa T = 230 °C m cat = 0.01 – 0.15 g Treatment & testing conditions Acid treatment has negative effect on the activity of MFI type zeolites FER treated sample shows improved activity due to increase in acid concentration and topology transformation.  Little change in selectivity – conversion realtion for MFI type zeolite  Large change – trends are similar to these found for MFI types XRD show transformation after calcination  Topology effect between FER and MFI FER Untreated Acid Treated (AT) Topology transformation 1Acid leaching removes framework alumina but induces, in addition of NH 4 + exchange and calcination, extra acid sites which are rapidly deactivated 2Framework transformation is triggered within FER type of zeolites when calcined after acid treatment is performed 3Most promising zeolite for the dehydration towards butenes is untreated MFI: Highest activity, low selectivity towards ether at high conversions and high stability Activity