Production of diesel-type biofuel by conversion of gamma-valerolactone over noble metalbased bifunctional catalysts

MARTÍNEZ FIGUEREDO, KARLA G.; SEGOBIA, DARÍO J.; BERTERO, NICOLÁS MAXIMILIANO

Santa Fe

Workshop; French Argentinean Workshop on Heterogeneous Catalysis; 2023

INCAPE-IC2MP

In the last decades approximately 28% of the total energy demand was employed for transportation purposes. However, 92% of this energy was supplied by fossil fuels and this is causing serious environmental problems. Lignocellulosic biomass has been targeted as a promising raw material for the production of biofuels because: 1) is a non-edible biomass; 2) is an abundant and inexpensive form of biomass. The strategy for producing biofuels from biomass comprises: (a) conversion of lignocellulose into platform molecules such as levulinic acid (LA) and -valerolactone (GVL); (b) transformation of these platforms into biofuels [1]. Valeric esters have been regarded as attractive biofuels due to their considerably energy density, good volatility-ignition properties and appropriate polarity in comparison with current biofuels and passed satisfactorily a 250,000 km road trial [2]. Particularly, pentyl valerate (PV) has a higher volatility, better cold-flow properties and lubricity than FAME and engine efficiency and emissions are not strongly affected when it is blended with diesel up to 20%.In the last decades approximately 28% of the total energy demand was employed for transportation purposes. However, 92% of this energy was supplied by fossil fuels and this is causing serious environmental problems. Lignocellulosic biomass has been targeted as a promising raw material for the production of biofuels because: 1) is a non-edible biomass; 2) is an abundant and inexpensive form of biomass. The strategy for producing biofuels from biomass comprises: (a) conversion of lignocellulose into platform molecules such as levulinic acid (LA) and -valerolactone (GVL); (b) transformation of these platforms into biofuels [1]. Valeric esters have been regarded as attractive biofuels due to their considerably energy density, good volatility-ignition properties and appropriate polarity in comparison with current biofuels and passed satisfactorily a 250,000 km road trial [2]. Particularly, pentyl valerate (PV) has a higher volatility, better cold-flow properties and lubricity than FAME and engine efficiency and emissions are not strongly affected when it is blended with diesel up to 20%.In the last decades approximately 28% of the total energy demand was employed for transportation purposes. However, 92% of this energy was supplied by fossil fuels and this is causing serious environmental problems. Lignocellulosic biomass has been targeted as a promising raw material for the production of biofuels because: 1) is a non-edible biomass; 2) is an abundant and inexpensive form of biomass. The strategy for producing biofuels from biomass comprises: (a) conversion of lignocellulose into platform molecules such as levulinic acid (LA) and -valerolactone (GVL); (b) transformation of these platforms into biofuels [1]. Valeric esters have been regarded as attractive biofuels due to their considerably energy density, good volatility-ignition properties and appropriate polarity in comparison with current biofuels and passed satisfactorily a 250,000 km road trial [2]. Particularly, pentyl valerate (PV) has a higher volatility, better cold-flow properties and lubricity than FAME and engine efficiency and emissions are not strongly affected when it is blended with diesel up to 20%.There are two possible routes for obtaining PV from GVL (Figure 1). ROUTE 1 is based on hydrogenation/hydrogenolysis of GVL to pentanoic acid (PA) and subsequent esterification of PA with pentanol (PL), where Brønsted acid sites are required. ROUTE 2 involves the transesterification of PL to the carboxylic group of the GVL to form 4-hydroxy pentyl valerate (HPV), dehydration of HPV to pentyl 2-pentenoate (PP), where Lewis acidity is necessary, and finally hydrogenation of PP to PV. However, other products such as 4-pentoxy pentyl valerate (PPV) and PA can be formed [3]. The aim of this work was to correlate the acid properties of noble metal-based catalysts with their catalytic performance in the PV production from GVL, PL and H2 following ROUTE 2.The motivation of this work relies on the necessity of boosting the PV productivity in these batch one-pot processes before considering continuous processes.