The catalytic hydrotreatment of Kraft lignin using sulfided NiMo and CoMo catalysts on different acidic and basic supports (Al ₂ O ₃ , ZSM-5, activated carbon (AC) and MgO-La ₂ O ₃ ) was studied in the absence of a solvent.

Efficient catalytic hydrotreatment of Kraft lignin to yield aromatic monomers was demonstrated in supercritical methanol using a variety of NiW and NiMo catalysts on acidic, basic and neutral supports. It was found that NiW catalysts on neutral or basic supports are highly suitable for depolymerization of Kraft lignin to methanol soluble organics in high yields at 320 °C and 35 bar H₂ pressure. An extensive analysis of the product mixtures was carried out using GC-MS-FID, GC × GC-FID, 2D HSQC NMR, GPC and elemental analysis, and several techniques were used for the characterization of the prepared catalysts in order to determine the acidity and basicity of the support and morphological changes after the catalytic reaction. The best results were obtained with sulphided NiW catalysts supported on activated carbon. Efficient depolymerization of Kraft lignin and a total 28 wt% monomer yield was obtained within 8 h and 76% of the products were alkylphenolics and guaiacolics. Over prolonged reaction times, the total monomer yield reached 35 wt%, containing up to 26 wt% alkylphenolics. During catalytic processing, deoxygenation was the most prevalent reaction and, importantly, no competing aromatic ring hydrogenation or undesired repolymerization to insoluble char was observed. The catalytic system described here represents a highly efficient and selective method for the production of alkylphenolics and guaiacolics from Kraft lignin.

The literature from the past few years dealing with hydrodesulfurization catalysts to deeply remove the sulfur-containing compounds in fuels is reviewed in this communication. We focus on the typical transition metal sulfides (TMS) Ni/Co-promoted Mo, W-based bi- and tri-metallic catalysts for selective removal of sulfur from typical refractory compounds. This review is separated into three very specific topics of the catalysts to produce ultra-low sulfur diesel. The first issue is the supported catalysts; the second, the self-supported or unsupported catalysts and finally, a brief discussion about the theoretical studies. We also inspect some details about the effect of support, the use of organic and inorganic additives and aspects related to the preparation of unsupported catalysts. We discuss some hot topics and details of the unsupported catalyst preparation that could influence the sulfur removal capacity of specific systems. Parameters such as surface acidity, dispersion, morphological changes of the active phases, and the promotion effect are the common factors discussed in the vast majority of present-day research. We conclude from this review that hydrodesulfurization performance of TMS catalysts supported or unsupported may be improved by using new methodologies, both experimental and theoretical, to fulfill the societal needs of ultra-low sulfur fuels, which more stringent future regulations will require.