Catalytic upgrading of bio-oil from halophyte seeds into transportation fuels

Abstract

Because of socioeconomic considerations, wide-scale production of biofuel necessitates the utilization of nonedible biomass feedstock that does not compete for land and fresh water resources. In this regard, Salicornia bigelovii (SB) is the most investigated halophyte species. The high oil content in SB seeds has sparked mounting research that aims to utilize SB as an industrial crop in the production of bio-oil, particularly in coastal areas where these plants thrive. However, the oil extracted from the pyrolysis of raw SB seeds is largely dominated by oxygenated fatty acids, most notably 9,12-octadecadienoic acid and 9,17-octadecadienal, typical to that of other crops. The pyrolysate bio-oil of the raw SB seeds exhibited a relative yield of oxygenated compounds that decreased from 57.05 % at 200 °C to 9.81 % at 500 °C, and the relative yield of nitrogenated compounds increased from 4.86 % at 200 °C to 21.97 % at 500 °C. To improve the quality of the produced bio-oil, herein we investigated the catalytic hydrodeoxygenation (HDO) of the fragments that were produced from the thermal degradation of SB seeds. A 5 %Ni–CeO2 catalyst was prepared and characterized by a wide array of methods X-ray diffraction, X-ray photoelectron spectroscopy, temperature programmed reduction, scanning electron microscope, Brunauer-Emmett-Teller analysis, and thermogravimetric analyzer. The catalytic run was executed between 200 and 500 °C in a flow reactor. The deployed catalytic methodology displayed a profound HDO capacity. At 400 °C, for instance, the gas chromatography mass spectroscopy (GC–MS) detected loads of paraffin and aromatic compounds exists at appreciable values of 48.0 % and 28.5 %, respectively. With a total relative yield of 43.2 % (at 400 °C), C8–C15 species (i.e., jet fuel fractions) were the most abundant species in the upgraded SB bio-oil. The release of H2, CO, CO2, and CH4 was analyzed qualitatively and quantitatively using gas chromatography thermal conductivity detector and Fourier infrared spectroscopic analysis. When the Ni–CeO2 catalyst was utilized, a complete deoxygenated bio-oil was obtained from SB seeds using the surface-assisted HDO reaction. On the basis of the elemental analysis, the biochar's hydrogen and oxygen contents were found to decrease significantly. Density functional theory computations showed mechanisms for reactions that underpinned the experimentally observed hydrodeoxygenation process. Outcomes presented herein shall be instrumental toward the effective utilization of halophyte in the production of commercial transportation fuels.