Role of oxophilic metal ions (Mo, Zr, Ti) impregnated Ni/γ-Al2O3 catalysts for hydrothermal liquefaction of kraft lignin

Abstract

In this study, the effect of oxophilic metal ions (Mo, Zr, and Ti) loaded Ni/γ-Al2O3 (Al) catalysts was explored for the first time for the hydrothermal liquefaction of kraft lignin using IPA for 30 min/280 °C. The liquefaction of lignin was noticed to be 65.4 wt% with 10 wt% loaded Ni/Al with an 81.3% total conversion. The performance of Ni/Al was enhanced remarkably by using the oxophilic metal ions as promoters owing to an increase in the Lewis character of the catalyst's surface. The bio-oil yield was a maximum of 72 wt% with a 91.5% conversion using 3 wt% loaded Ti–10Ni/Al. The different alcoholic solvents such as methanol, ethanol, and IPA were also examined for the same. However, the best liquefaction was noticed with IPA owing to better H-donor tendency. Additionally, a series of IPA-water co-solvent examinations attributed to a significant improvement in the liquefaction to 74.8 wt% (50:50) IPA-water system. The optimum catalyst 10Ni–3Ti/Al was tested for four catalytic cycles, which indicated a slight loss in the catalytic activity because of blockage of the catalytic active site by char deposition. The GC-MS investigation of optimum catalytic bio-oil showed the highest selectivity of acetosyringone (68.5%) and 2-methoxy-phenol (22.8%), which was observed to be only 30.1 and 5.1% for non-catalytic bio-oil. The 1H NMR and FT-IR investigation of raw lignin and bio-oil proved the breakage of lignin's 3D structure into respective G-and S-type monomeric compounds. Additionally, catalysts were characterized using the XRD, BET, and XPS analysis.