Micro/mesoporous LTL derived materials for catalytic transfer hydrogenation and acid reactions of bio-based levulinic acid and furanics

resumo

The biomass-derived platform chemicals furfural and 5-(hydroxymethyl)furfural (HMF) may be converted to alpha-angelica lactone (AnL) and levulinic acid (LA). Presently, LA (synthesized from carbohydrates) has several multinational market players. Attractive biobased oxygenated fuel additives, solvents, etc., may be produced from AnL and LA via acid and reduction chemistry, namely alkyl levulinates and gamma-valerolactone (GVL). In this work, hierarchical hafnium-containing multifunctional Linde type L (LTL) related zeotypes were prepared via top-down strategies, for the chemical valorization of LA, AnL and HMF via integrated catalytic transfer hydrogenation (CTH) and acid reactions in alcohol medium. This is the first report of CTH applications (in general) of LTL related materials. The influence of the post-synthesis treatments/conditions (desilication, dealumination, solid-state impregnation of Hf or Zr) on the material properties and catalytic performances was studied. AnL and LA were converted to 2-butyl levulinate (2BL) and GVL in high total yields of up to ca. 100%, at 200 ?, and GVL/2BL molar ratios up to 10. HMF conversion gave mainly the furanic ethers 5-(sec-butoxymethyl)furfural and 2,5-bis(sec-butoxymethyl)furan (up to 63% total yield, in 2-butanol at 200 ?/24 h). Mechanistic, reaction kinetics and material characterization studies indicated that the catalytic results depend on a complex interplay of different factors (material properties, type of substrate). The recovered-reused solids performed steadily.

palavras-chave

NONNOBLE METAL-CATALYSTS; GAMMA-VALEROLACTONE GVL; HETEROGENEOUS CATALYST; BIOMASS DERIVATIVES; PHASE HYDROGENATION; MESOPOROUS SILICA; BETA ZEOLITES; FORMIC-ACID; CONVERSION; ESTERS

categoria

Chemistry

autores

Antunes, MM; Silva, AF; Fernandes, A; Ribeiro, F; Neves, P; Pillinger, M; Valente, AA

Grupos

G1 - Materiais Porosos e Nanossistemas
G4 - Materiais Renováveis e Economia Circular

Projectos

CICECO - Aveiro Institute of Materials (UIDB/50011/2020)

CICECO - Aveiro Institute of Materials (UIDP/50011/2020)

Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)

Conversao catalitica de olefinas derivadas da biomassa (BiOle_AcidOxCat)

Rede Nacional de Ressonância Magnética Nuclear (PTNMR)

agradecimentos

This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020, financed by national funds through the FCT/MEC (PIDDAC). The positions held by MMA and AF were funded by national funds (OE), through FCT, IP, in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of article 23 of the Decree-Law 57/2016 of 29 August, changed by Law 57/2017 of 19 July. The position held by AFS was funded by Project POCI-01-0145-FEDER-030075 (COMPETE 2020 Operational Thematic Program for Competitiveness and Internationalization) co-financed by national funds through the FCT/MCTES and the European Union through the European Regional Development Fund under the Portugal 2020 Partnership Agreement. The NMR spectrometer used is part of the National NMR Network (PTNMR) and is partially supported by Infrastructure Project No 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC).