The catalytic hydrotreatment of Kraft lignin using sulfided NiMo and CoMo catalysts on different acidic and basic supports (Al2O3, ZSM-5, activated carbon (AC) and MgO-La2O3) was studied in the absence of a solvent. Experiments were carried out in a batch set-up at a reaction temperature of 350 °C, 4 h and 100 bar initial H2 pressure. The catalysts before and after reaction were characterized by X-ray diffraction, temperature programmed desorption of ammonia/CO2, BET surface area and scanning electron microscopy. The liquid products were fractionated and analyzed extensively by different techniques such as GPC, GC-MS-FID, GC-TCD, FT-IR, 13 C-NMR and elemental analyses. Two dimensional gas chromatography (GCxGC-FID) was applied to identify distinct groups of compounds (aromatics, alkylphenolics, alkanes) after reaction, and product quantification was performed based on this method. Catalyst activity is a function of the support and increased in the order Al2O3 < ZSM-5 < AC=MgO-La2O3. In addition, the support also largely influenced the extent of depolymerization and monomer yield. The highest lignin oil yields were obtained using the sulfided NiMo supported on activated carbon and MgO-La2O3. The highest total monomer yield 26.4 wt.% on lignin intake, which included 15.7 wt.% alkyl-phenolics was obtained using the sulfided NiMo/MgO-La2O3 catalyst.

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.

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.

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Limonite, a low-cost iron ore, was investigated as a potential hydrotreatment catalyst for kraft lignin without the use of an external solvent (batch reactor, initial H2 pressure of 100 bar, 4 h). The best results were obtained at 450 °C resulting in 34 wt % of liquefied kraft lignin (lignin oil) on lignin intake. The composition of the lignin oil was determined in detail (elemental composition, GC-MS, GC×GC-FID, and GPC). The total GC-detectable monomeric species amounts up to 31 wt % on lignin intake, indicating that 92 wt % of the products in the lignin oil are volatile and thus of low molecular weight. The lignin oil was rich in low-molecular-weight alkylphenolics (17 wt % on lignin) and aromatics (8 wt % on lignin). Performance of the limonite catalyst was compared to other Fe-based catalysts (goethite and iron disulfide) and limonite was shown to give the highest yields of alkylphenolics and aromatics. The limonite catalyst before and after reaction was characterized using XRD, TEM, and nitrogen physisorption to determine changes in structure during reaction. Catalyst recycling tests were performed and show that the catalyst is active after reuse, despite the fact that the morphology changed and that the surface area of the catalyst particles was decreased. Our results clearly reveal that cheap limonite catalysts have the potential to be used for the depolymerization/hydrodeoxygenation of kraft lignin for the production of valuable biobased phenolics and aromatics.

The conversion of lignin to biofuels and biobased chemicals is currently attracting a lot of attention. We here report on the valorization of Kraft lignin by a catalytic hydrotreatment using Ni, Mo, and W phosphide catalysts supported on activated carbon in the absence of an external solvent. Experiments were carried out in a batch setup in the temperature range of 400–500 °C and 100 bar initial H2 pressure. The synthesized catalysts were characterized by X-ray diffraction, nitrogen physisorption, and transmission electron microscopy. The lignin oils were analyzed extensively by different techniques such as GPC, GC-MS-FID, 13C NMR, and elemental analysis. Two-dimensional gas chromatography (GC×GC-FID) was applied to identify and quantify distinct groups of compounds (aromatics, alkylphenolics, alkanes, etc.). Mo-based catalysts displayed higher activity compared to the W-containing catalysts. The reaction parameters such as the effect of reaction temperature, reaction time, and catalyst loading were studied for two catalysts (15MoP/AC and 20NiMoP/AC), and optimized reaction conditions regarding yields of monomeric components were identified (400 °C, 100 bar H2 at RT, 10 wt % catalyst loading on lignin intake). The highest monomer yield (45.7 wt % on lignin) was obtained for the 20NiMoP/AC (Ni 5.6 wt %, Mo 9.1 wt %, P 5.9 wt %) catalyst, which includes 25% alkylphenolics, 8.7% aromatics, and 9.9% alkanes. Our results clearly reveal that the phosphide catalysts are highly efficient catalyst to depolymerize the Kraft lignin to valuable biobased chemicals and outperform sulfided NiMo catalysts (monomer yield on lignin < 30 wt %).

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This article reviews the current state and development of thermal catalytic processes using transition metals (TM) supported on zeolites (TM/Z), as well as the contribution of theoretical studies to understand the details of the catalytic processes. Structural features inherent to zeolites, and their corresponding properties such as ion exchange capacity, stable and very regular microporosity, the ability to create additional mesoporosity, as well as the potential chemical modification of their properties by isomorphic substitution of tetrahedral atoms in the crystal framework, make them unique catalyst carriers. New methods that modify zeolites, including sequential ion exchange, multiple isomorphic substitution, and the creation of hierarchically porous structures both during synthesis and in subsequent stages of post-synthetic processing, continue to be discovered. TM/Z catalysts can be applied to new processes such as CO2 capture/conversion, methane activation/conversion, selective catalytic NOx reduction (SCR-deNOx), catalytic depolymerization, biomass conversion and H2 production/storage.