The use of agricultural residues for the production of bio-oil is an important alternative to the use of fossil fuels. In this study, the Caupi bean pod (Vigna unguiculata) was characterized and used as biomass in the production of bio-oil. This biomass was evaluated in terms of physicochemical, morphological (scanning electron microscopy (SEM)), and thermal (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) characterization, lignocellulosic composition, and pyrolysis processes. The pyrolysis was carried out in a stainless steel fixed-bed reactor (260 mm in length and 60 mm in diameter) under atmospheric nitrogen pressure. Pyrolysis was conducted at 550, 600, and 700 °C and N 2 gas flow of 2, 5, and 7 mL min-1. The chemical composition of the bio-oils was studied through CHN, TGA, Fourier-transform infrared spectroscopy (FTIR), and gas chromatography-mass spectrometry (GC-MS). The results confirmed the bean pod's potential in the thermochemical process. The thermogravimetric analyses demonstrate that there can be a relationship between the components of the principal biomass (cellulose, hemicellulose, and lignin) and the compounds present in the bio-oil. The obtained bio-oils represent bio-products that are rich in compounds of several chemical classes with relevant commercial value such as acids (palmitic, linoleic, oleic, and stearic), alcohols (ethylene glycol), sugars (levoglucosan), and phenols (guaiacol, catechol, phenol, and pyrocatechol).
Ultrasonic pretreatment of cowpea bean pod biomass with addition of tripotassium phosphate (K3PO4) was used to induce the production of bio-oil enriched in phenolic compounds. An ultrasound bath operating at 40 kHz, 154 W power, and constant biomass:K3PO4 ratio of 5:1 (m/m) was used for pretreatments with different durations: 0.5, 1.5, 3, 6, 8, and 12 h. After the pretreatment, the biomass was pyrolyzed in a fixed bed reactor at 600 °C, under a flow of N2 at 5 mL min-1. The pyrolysis results indicated that the use of K3PO4 reduced the bio-oil yield, when compared to non-catalytic pyrolysis, and that the use of ultrasound caused increased biomass devolatilization, increasing the gas yield and reducing the formation of biochar. Gas chromatography mass spectrometry (GC-MS) analysis of the bio-oils indicated that pretreatment of the biomass led to significant increases of the phenolics contents, as well as alteration of the chemical profile of these compounds. The highest phenolics content of 8.12% m/m was obtained for the biomass submitted to 1.5 h of ultrasonic pretreatment, compared to 4.89% m/m for the untreated biomass.
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