Renewable hydrogen production by aqueous phase reforming (APR) over Ni/Al-Ca catalysts was studied using pure or refined crude glycerol as feedstock. The APR was carried out in a fixed bed reactor at 238 °C, 37 absolute bar for 3 h, using a solution of 5 wt.% of glycerol, obtaining gas and liquid products. The catalysts were prepared by the co-precipitation method, calcined at different temperatures, and characterized before and after their use by several techniques (XRD, ICP-OES, H₂-TPR, NH₃-TPD, CO₂-TPD, FESEM, and N₂-physisorption). Increasing the calcination temperature and adding Ca decreased the surface area from 256 to 188 m²/g, and its value after the APR changed depending on the feedstock used. The properties of the acid and basic sites of the catalysts influenced the H₂ yield also depending on the feed used. The Ni crystallite was between 6 and 20 nm. In general, the incorporation of Ca into Ni-based catalysts and the increase of the calcination temperature improved H₂ production, obtaining 188 mg H₂/mol C fed during the APR of refined crude glycerol over Ni/AlCa-675 catalyst, which was calcined at 675 °C. This is a promising result from the point of view of enhancing the economic viability of biodiesel.

Bio-oil obtained from biomass pyrolysis has great potential for several applications after being upgraded and refined. This study established a method for separating bio-oil into different fractions based on polarity and molecular size to extract phenolic and polyphenolic compounds with antioxidant properties. The fractions were analyzed using various spectroscopic and chromatographic techniques, such as GC/MS, FTIR, UV-vis, SEC, DOSY-NMR, ¹³C-NMR, and ³¹P-NMR. The antioxidant properties of these fractions were tested by examining their ability to improve the oxidative stability of biodiesel. The results strongly connected the bio-oil's chemical functionalities and antioxidant power. During solvent fractionation, dichloromethane could extract phenolic structures, which were subsequently size-fractionated. The subfractions with lower molecular weight (in the order of monomers and dimers) outperformed the antioxidant potential of the crude bio-oil. Heavier subfractions from dichloromethane extraction did not show good antioxidant abilities, which was related to the low hydroxy group content. After solvent extraction, phenolic oligomers remained in the water-insoluble/dichloromethane-insoluble fraction, which showed good antioxidant potential despite its low solubility in biodiesel.

The present work summarizes the results of an experimental study focused on producing antioxidant additives for biofuels from argan shell lignin. The generation of this waste has noticeably increased in specific regions of Morocco as a result of the upward trend in the production of argan oil. Lignin extracted from argan shells via a semi-chemical pulping process was depolymerized under hydrothermal conditions in a stirred autoclave reactor at a temperature range of 250–350 °C. Lignin conversion to phenolic compounds was conducted in subcritical water together with different reaction medium (H₂, CO₂, and HCOOH). The organic fraction in the aqueous liquid product was extracted and blended with biodiesel at a dosage of 1 wt % to evaluate its antioxidant potential. According to the obtained results, the biodiesel oxidation stability time was drastically improved up to 400%. The depolymerization temperature was observed as a critical factor in the antioxidant potential of the additives, showing a maximum value at 300 °C, regardless of the reaction medium. An extensive characterization of the produced additives was performed. The phenolic monomers present in the produced additives were identified using gas chromatography–mass spectrometry, finding a notable presence of catechol, especially in the additives obtained at 300 °C, which led to the best results of biodiesel oxidation stability. Gel permeation chromatography analyses of the additives also showed a well dissolution of relatively big molecules (up to 7000 Da) in biodiesel. More efforts are required to verify the actual antioxidant potential of these types of molecules.

The effect of catalyst loading in the Aqueous Phase Reforming (APR) of bio-oil aqueous fraction has been studied with a Ni-Co/Al-Mg coprecipitated catalyst. Because of the high content of water in the bio-oil aqueous fraction, APR could be a useful process to convert this fraction into valuable products. Experiments of APR with continuous feeding of aqueous solution of acetol, butanol and acetic acid as the only compound, together with a simulated and a real aqueous fraction of bio-oil, were carried out. Liquid products in the liquid effluent of the APR model compounds were quantified and the reaction pathways were revised. The increase of catalyst loading produced an increase of gas production and a gas with higher alkanes content. Acetol was the compound with the highest reactivity while the conversion of acetic acid was very low. The presence of acetic acid in the feed caused catalyst deactivation.

The present work studied the stability and reusability of Ni/Al-Fe catalyst in the aqueous phase hydrogenolysis of glycerol without external hydrogen addition. The catalyst based on 28 molar % of Ni with 3/1 molar ratio of Al/Fe was prepared through co-precipitation. This catalyst presented the best performance in our last study which compares several Ni/Al-Fe catalysts with different molar ratios of Al/Fe. To see the influence of the pressurized water on the physicochemical characteristics of Ni/Al-Fe catalyst, a test of up to 9 h has been carried out. Fresh and used catalysts were characterized by various techniques: X-ray Diffraction (XRD), N₂-physisorption, field emission scanning electron microscopy (FESEM) and STEM. Glycerol conversion and carbon yield to gases and liquids did not vary significantly when compared at 3 h and 9 h. Furthermore, the morphology of the catalyst remains stable after continuous recycling under severe hydrothermal conditions. The nickel rich phase of the catalyst, which was determined by XRD and scanning transmission electron microscopy (STEM) techniques, showed a stable size after 9 h under reaction.

The 21st century arrived with global growth of energy demand caused by population and standard of living increases. In this context, a suitable alternative to produce COx-free H₂ is the catalytic decomposition of methane (CDM), which also allows for obtaining high-value-added carbonaceous nanomaterials (CNMs), such as carbon nanotubes (CNTs). This work presents the results obtained in the co-production of CO_x-free hydrogen and CNTs by CDM using Ni–Cu and Co–Cu catalysts supported on carbon derived from Argan (Argania spinosa) shell (ArDC). The results show that the operation at 900 °C and a feed-ratio CH₄:H₂ = 2 with the Ni–Cu/ArDC catalyst is the most active, producing 3.7 g_C/g_metal after 2 h of reaction (equivalent to average hydrogen productivity of 0.61 g H₂/g_metal∙h). The lower productivity of the Co–Cu/ArDC catalyst (1.4 g_C/g_metal) could be caused by the higher proportion of small metallic NPs (<5 nm) that remain confined inside the micropores of the carbonaceous support, hindering the formation and growth of the CNTs. The TEM and Raman results indicate that the Co–Cu catalyst is able to selectively produce CNTs of high quality at temperatures below 850 °C, attaining the best results at 800 °C. The results obtained in this work also show the elevated potential of Argan residues, as a representative of other lignocellulosic raw materials, in the development of carbonaceous materials and nanomaterials of high added-value.