Hydrodeoxygenation of methyl heptanoate and phenol over sulphided supported NiMo and CoMo catalysts

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.advisor Krause, Outi, Prof.
dc.contributor.author Turpeinen, Eeva-Maija
dc.date.accessioned 2012-08-31T07:42:13Z
dc.date.available 2012-08-31T07:42:13Z
dc.date.issued 2011
dc.identifier.isbn 978-952-60-4272-5 (PDF)
dc.identifier.isbn 978-952-60-4271-8 (printed)
dc.identifier.issn 1799-4942
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/5021
dc.description.abstract Biomass-based energy sources are under intensive study for replacing fossil fuels with environmentally friendly alternatives. Bio-oils, intended for use as such or mixed with fossil fuels, need to be upgraded by hydrodeoxygenation (HDO) due to the high oxygen-content of the molecules, which causes unwanted fuel properties. This thesis describes oxygen removal reactions of methyl heptanoate and phenol over sulphided NiMo/γ-Al2O3 and CoMo/γ-Al2O3 catalysts. These two components were chosen as representative model reactants of the complex bio-oils. Reaction schemes for the HDO of methyl heptanoate and phenol are presented. Reaction steps were justified with acid-catalysed reactions (hydrolysis, dehydration, esterification), reductive reactions and decarbonylation. Reactivity of the reactants individually and as a mixture and their product distributions were explored with and without a sulphur additive as sulphur is needed to keep the catalyst in the sulphided form. Sulphur-containing components were formed during the HDO reactions even without sulphur addition during the experiments. The source of the sulphur is the sulphur species attached to the catalyst surface. Possible active sites are also discussed. Reduction reactions were proposed to occur on coordinatively unsaturated sites (CUS), whereas acid-catalysed reactions and decarbonylation need sulphur-saturated sites. The vapour-liquid equilibrium (VLE) of methyl heptanoate and solvent, in this case m-xylene, was measured to improve composition analysis of the multi-phase system. The Predictive Soave-Redlich-Kwong (PSRK) model was shown to be a good tool for simulation of the gas phase of a non-ideal system with polar components. The findings give new insights into the HDO reactions by describing the reaction pathways of two different types of model components and how the sulphur species affect those pathways. Moreover, the performance of the sulphided catalyst and simulation of a non-ideal system are presented. en
dc.format.extent Verkkokirja ( KB, 99 s.)
dc.format.mimetype application/pdf
dc.language.iso en en
dc.publisher Aalto University en
dc.relation.ispartofseries Aalto University publication series DOCTORAL DISSERTATIONS , 78/2011 en
dc.relation.haspart [Publication 1]: Eeva-Maija Turpeinen, Erlin Sapei, Petri Uusi-Kyyny, Kari I. Keskinen, and Outi A. I. Krause. 2011. Finding a suitable thermodynamic model and phase equilibria for hydrodeoxygenation reactions of methyl heptanoate. Fuel, volume 90, number 11, pages 3315-3322. en
dc.relation.haspart [Publication 2]: O. İ. Şenol, E.-M. Ryymin, T.-R. Viljava, and A. O. I. Krause. 2007. Reactions of methyl heptanoate hydrodeoxygenation on sulphided catalysts. Journal of Molecular Catalysis A: Chemical, volume 268, numbers 1-2, pages 1-8. en
dc.relation.haspart [Publication 3]: Eeva-Maija Ryymin, Maija L. Honkela, Tuula-Riitta Viljava, and A. Outi I. Krause. 2009. Insight to sulfur species in the hydrodeoxygenation of aliphatic esters over sulfided NiMo/γ-Al2O3 catalyst. Applied Catalysis A: General, volume 358, number 1, pages 42-48. en
dc.relation.haspart [Publication 4]: O. İ. Şenol, E.-M. Ryymin, T.-R. Viljava, and A. O. I. Krause. 2007. Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts. Journal of Molecular Catalysis A: Chemical, volume 277, numbers 1-2, pages 107-112. en
dc.relation.haspart [Publication 5]: Eeva-Maija Ryymin, Maija L. Honkela, Tuula-Riitta Viljava, and A. Outi I. Krause. 2010. Competitive reactions and mechanisms in the simultaneous HDO of phenol and methyl heptanoate over sulphided NiMo/γ-Al2O3. Applied Catalysis A: General, volume 389, numbers 1-2, pages 114-121. en
dc.subject.other Chemistry
dc.subject.other Energy
dc.title Hydrodeoxygenation of methyl heptanoate and phenol over sulphided supported NiMo and CoMo catalysts en
dc.type G5 Artikkeliväitöskirja fi
dc.contributor.school Kemian tekniikan korkeakoulu fi
dc.contributor.department Biotekniikan ja kemian tekniikan laitos fi
dc.contributor.department Department of Biotechnology and Chemical Technology en
dc.subject.keyword hydrodeoxygenation (HDO) en
dc.subject.keyword methyl heptanoate en
dc.subject.keyword phenol en
dc.subject.keyword active sites en
dc.subject.keyword vapour-liquid equilibrium en
dc.identifier.urn URN:ISBN:978-952-60-4272-5
dc.type.dcmitype text en
dc.type.ontasot Väitöskirja (artikkeli) fi
dc.type.ontasot Doctoral dissertation (article-based) en
dc.contributor.supervisor Krause, Outi, Prof.


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