Journal
BIOMASS CONVERSION AND BIOREFINERY
Volume 7, Issue 3, Pages 331-342Publisher
SPRINGER HEIDELBERG
DOI: 10.1007/s13399-017-0254-x
Keywords
Esterification; Bio-oil; Pyrolysis; Heterogeneous catalysis
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Funding
- EPSRC [EP/K000616/2, EP/G007594/4, EP/K036548/2, EP/N009924/1]
- Leadership Fellowship
- Royal Society
- European Union Seventh Framework Programme (FP7) [604307]
- EPSRC [EP/G007594/4, EP/N009924/1, EP/K036548/2, EP/K000616/2] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/N009924/1] Funding Source: researchfish
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A family of faujasite (FAU) zeolites with different Si:Al ratio, and/or hierarchical porosity introduced via post-synthetic alkaline desilication treatment, have been evaluated as solid acid catalysts for esterification pretreatments of pyrolysis bio-oil components. Acetic acid esterification with aliphatic and aromatic alcohols including methanol, anisyl alcohol, benzyl alcohol, p-cresol and n-butanol was first selected as a model reaction to identify the optimum zeolite properties. Materials were fully characterised using N-2 porosimetry, ICP, XRD, XPS, FT-IR, pyridine adsorption, NH3 TPD, In-situ ATR and inverse gas chromatography (IGC). IGC demonstrates that the surface polarity and hence hydrophobicity of FAU decreases with increased Si:Al ratio. Despite possessing a higher acid site loading and acetic acid adsorption capacity, high Al-content FAU possess weaker acidity than more siliceous catalysts. Esterification activity increases with acid strength and decreasing surface polarity following the order FAU30 > FAU6 > FAU2.6. The introduction of mesoporosity through synthesis of a hierarchical HFAU30 material further enhances esterification activity through improved acid site accessibility and hydrophobicity. Methanol was the most reactive alcohol for esterification, and evaluated with HFAU30 for the pretreatment of a real pyrolysis bio-oil, reducing the acid content by 76% under mild conditions.
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