Arjan Kloekhorst

Solvent free depolymerization of Kraft lignin to alkyl-phenolics using supported NiMo and CoMo catalysts

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, 13C-NMR and elemental analyses. Two dimensional gas chromatography (GC × GC-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.

Catalytic hydrotreatment of pyrolytic lignins to give alkylphenolics and aromatics using a supported Ru catalyst

The catalytic hydrotreatment of two pyrolytic lignins (pine and forestry residue), obtained from the corresponding fast pyrolysis oils, and organosolv Alcell lignin as a benchmark was explored in a batch set-up using Ru/C as the catalyst (400 °C, 4 h, 100 bar initial H2 pressure). The highest lignin oil yield was obtained for forest residue pyrolytic lignin (>75 wt% on intake). Advanced GCxGC techniques in combination with GPC and 13C-NMR measurements indicate that the lignin oils contain high amounts of interesting monomeric chemicals like alkylphenolics (up to 20.5 wt% on lignin feed intake) and aromatics (up to 14.1 wt% on lignin feed intake). These values are considerably higher than for Alcell lignin (6.6 wt% alkylphenolics and 9.7 wt% aromatics) and clearly indicate that pyrolytic lignins have potential to be used as feeds for the production of biobased phenolics and aromatics.

Catalytic Hydrotreatment of Humins in Mixtures of Formic Acid/2-Propanol with Supported Ruthenium Catalysts

The catalytic hydrotreatment of humins, which are the solid byproducts from the conversion of C6 sugars (glucose, fructose) into 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), by using supported ruthenium catalysts has been investigated. Reactions were carried out in a batch setup at elevated temperatures (400 °C) by using a hydrogen donor (formic acid (FA) in isopropanol (IPA) or hydrogen gas), with humins obtained from d-glucose. Humin conversions of up to 69 % were achieved with Ru/C and FA, whereas the performance for Ru on alumina was slightly poorer (59 % humin conversion). Humin oils were characterized by using a range of analytical techniques (GC, GC-MS, GCxGC, gel permeation chromatography) and were shown to consist of monomers, mainly alkyl phenolics (>45 % based on compounds detectable by GC) and higher oligomers. A reaction network for the reaction is proposed based on structural proposals for humins and the main reaction products.

Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach

Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols, catechols and, optionally, syringols in addition to alkylphenols. HDO with heterogeneous catalysts (Ru/C, CoMo/alumina, phosphided NiMO/C) effectively directed the product mixture towards alkylphenols by, among others, demethoxylation. Up to 15wt% monomeric aromatics of which 11wt% alkylphenols was obtained (on the lignin intake) with limited solid formation (<3wt% on lignin oil intake). For comparison, solid Kraft lignin was also directly hydrotreated for simultaneous depolymerisation and deoxygenation resulting in two times more alkylphenols. However, the alkylphenols concentration in the product oil is higher for the two-stage approach. Future research should compare direct hydrotreatment and the two-stage approach in more detail by techno-economic assessments.

Catalytic hydrotreatment of Alcell lignin fractions using a Ru/C catalyst

We here report the catalytic hydrotreatment of three different Alcell lignin fractions using a Ru/C catalyst in a batch reactor set-up (400 °C, 4 h, 100 bar H2 intake, 5 wt% catalyst on lignin). The fractions, obtained by a solvent fractionation scheme from Alcell lignin, differ in composition and molecular weight. The resulting product oils were characterized by various techniques, such as GC-MS-FID, GC × GC-FID, GPC, and 13C-NMR, to gain insight into the relationship between the feed and product yield/composition on a molecular level. The lowest molecular weight fraction (Mw = 660 g mol−1) gave the highest product oil yield after catalytic hydrotreatment (>70 wt% on lignin fraction). The main differences in molecular composition for the product oils were observed and are related to the chemical structure of the different feed fractions and less on the molecular weight. The highest amounts of valuable alkylphenolics (8.4 wt% on intake) and aromatic compounds (4.2 wt% on intake) in the product oils were obtained with the lowest molecular weight fraction. This fraction also contained the highest amounts of aliphatic hydrocarbons after the hydrotreatment reaction (14.0 wt% on intake), which were primarily linked to the presence of extractives in the Alcell lignin feed, that accumulate in this low molecular weight fraction during solvent fractionation.

Catalytic hydrotreatment of fast pyrolysis liquids in batch and continuous set-ups using a bimetallic Ni–Cu catalyst with a high metal content

In this paper, an experimental study on the hydrotreatment of fast pyrolysis liquids is reported in both batch and continuous set-ups using a novel bimetallic Ni–Cu based catalyst with high Ni loading (up to 50%) prepared by a sol–gel method. The experiments were carried out in a wide temperature range (80–410 °C) and at a hydrogen pressure between 100–200 bar to determine product properties and catalyst performance as a function of process conditions. To gain insight into the molecular transformations, the product oils were analysed by GC × GC, 1H-NMR and GPC and reveal that the sugar fraction is reactive in the low temperature range ( 300 °C). In addition, the organic acids are very persistent and reactivity was only observed above 350 °C. The results are rationalized using a reaction network involving competitive hydrogenation of reactive aldehydes and ketones of the sugar fraction of fast pyrolysis liquids and thermal polymerisation. In addition, relevant macro-properties of the product oils including flash point (30 to 80 °C), viscosity (0.06 to 0.93 Pa s) and TG residue (<1 to about 8 wt%) were determined and compared. Product oils with the lowest oxygen content (<13 wt%) were obtained in the continuous set-up at 410 °C.