Bio-oil is a promising source of chemicals and renewable fuels. As the liquid phase obtained from the pyrolysis of biomass, the composition and amount of bio-oil generated depend not only on the type of the biomass but also on the conditions under which pyrolysis is performed. Most fossil fuels can be replaced by bio-oil-derived products. Thus, bio-oil can be used directly or co-fed along with fossil fuels in boilers, transformed into fuel for car engines by hydrodeoxygenation or even used as a more suitable source for H2 production than biomass. On the other hand, due to its rich composition in compounds resulting from the pyrolysis of cellulose, hemicellulose and lignin, bio-oil co-acts as a source of various value-added chemicals such as aromatic compounds. This review presents an overview of the potential applications of bio-oils and the pyrolysis conditions under which they are obtained. Then, different extraction methods for value-added chemicals, along with the most recent developments, are discussed and future research directions for bio-oil upgrades are highlighted.

Olive stones are a by-product of the olive oil industry. In this work, the valorisation of olive stones through pyrolysis was attempted. Before pyrolysis, half of the samples were impregnated with sulphuric acid. Pyrolysis was carried out in a vertical tubular furnace with a ceramic support. The pyrolysis conditions assayed were: temperature between 400 and 600 °C, heating ramp between 5 and 20 °C∙min−1, and inert gas flow rate between 50 and 300 mL Ar∙min−1. Among them, temperature was the only parameter that influenced the pyrolysis product distribution. The most suitable temperature for obtaining biochar was 400 °C for both non-treated and pre-treated raw material, while for obtaining bio-oil, it was 600 °C for impregnated olive stones and 400 °C for the raw material. The impregnated olives stones led to bio-oils with much higher amounts of high-added-value products such as levoglucosenone and catechol. Finally, the biochars were impregnated with sulphuric acid and assayed as biocatalysts for the esterification of oleic acid with methanol in a stirred tank batch reactor at 60 °C for 30 min. Biochars from non-treated olive stones, which had lower specific surfaces, led to higher esterification yields (up to 96.2%).

Waste generated in the agri-food sector is a potential source of biomass and other products of high added value. In this work, the pyrolysis of orange waste and orange pruning was carried out to produce adsorbent biochars and characterise the bio-oils aiming for high-added-value compounds. Pyrolysis was carried out in a vertical tubular furnace on the laboratory scale modifying the temperature (400–600 °C), the heating ramp (5–20 °C·min−1) to reach the previous temperature and the inert gas flow rate (30–300 mL Ar·min−1) throughout the furnace. The most suitable conditions for obtaining biochar were found to be 400 °C, 5 °C·min−1, and 150 mL Ar·min−1 for orange waste, and 400 °C, 10 °C·min−1, and 150 mL Ar·min−1 for orange pruning. Thermogravimetric analysis showed higher thermal stability for orange pruning due to its higher lignin content (20% vs. 5% wt. on a wet basis). The bio-oil composition was determined by GC-MS. Toluene and 5-hydroxymethylfurfural were the main compounds found in orange waste bio-oils, while orange pruning bio-oils were composed mainly of 4-hydroxy-4-methyl-2-pentanone. Finally, the removal of the sulphur content from waste cooking oil was assayed with the biochars from both orange waste and orange pruning, whose BET surface areas were previously determined. Despite their low specific surface areas (≤1 m2·g−1 for orange waste biochars and up to 24.3 m2·g−1 for orange pruning biochars), these biochars achieved a reduction of the initial sulphur content of the waste cooking oil between 66.4% and 78.8%.