Douwe Sjirk Zijlstra

Aromatic monomers obtained by selective depolymerization of the lignin β‐O‐4 motif are typically phenolic and contain (oxygenated) alkyl substitutions. This work reveals the potential of a one‐pot catalytic lignin β‐O‐4 depolymerization cascade strategy that yields a uniform set of methoxylated aromatics without alkyl side‐chains. This cascade consists of the selective acceptorless dehydrogenation of the γ‐hydroxy group, a subsequent retro‐aldol reaction that cleaves the C _α −C _β bond, followed by in situ acceptorless decarbonylation of the formed aldehydes. This three‐step cascade reaction, catalyzed by an iridium(I)‐BINAP complex, resulted in 75 % selectivity for 1,2‐dimethoxybenzene from G‐type lignin dimers, alongside syngas (CO : H ₂ ≈1.4 : 1). Applying this method to a synthetic G‐type polymer, 11 wt % 1,2‐dimethoxybenzene was obtained. This versatile compound can be easily transformed into 3,4‐dimethoxyphenol, a valuable precursor for pharmaceutical synthesis, through an enzymatic catalytic approach. Moreover, the hydrodeoxygenation potential of 1,2‐dimethoxybenzene offers a pathway to produce valuable cyclohexane or benzene derivatives, presenting enticing opportunities for sustainable chemical transformations without the necessity for phenolic mixture upgrading via dealkylation.

Aromatic monomers obtained by selective depolymerization of the lignin β‐O‐4 motif are typically phenolic and contain (oxygenated) alkyl substitutions. This work reveals the potential of a one‐pot catalytic lignin β‐O‐4 depolymerization cascade strategy that yields a uniform set of methoxylated aromatics without alkyl side‐chains. This cascade consists of the selective acceptorless dehydrogenation of the γ‐hydroxy group, a subsequent retro‐aldol reaction that cleaves the C _α −C _β bond, followed by in situ acceptorless decarbonylation of the formed aldehydes. This three‐step cascade reaction, catalyzed by an iridium(I)‐BINAP complex, resulted in 75 % selectivity for 1,2‐dimethoxybenzene from G‐type lignin dimers, alongside syngas (CO : H ₂ ≈1.4 : 1). Applying this method to a synthetic G‐type polymer, 11 wt % 1,2‐dimethoxybenzene was obtained. This versatile compound can be easily transformed into 3,4‐dimethoxyphenol, a valuable precursor for pharmaceutical synthesis, through an enzymatic catalytic approach. Moreover, the hydrodeoxygenation potential of 1,2‐dimethoxybenzene offers a pathway to produce valuable cyclohexane or benzene derivatives, presenting enticing opportunities for sustainable chemical transformations without the necessity for phenolic mixture upgrading via dealkylation.

The ever-increasing volumes of food waste generated and the associated environmental issues require the development of new processing methods for these difficult waste streams. One of the technologies that can treat these waste streams directly is hydrothermal carbonization. In this work, olive pomace and orange peels were treated via a mild hydrothermal carbonization process (TORWASH^®) in a continuous-flow pilot plant. For olive pomace, a solid yield of 46 wt% and a dry matter content of 58% for the solid press cakes were obtained during continuous operation for 18 days. For orange peels, the values were lower with 31 wt% solid yield and a 42% dry matter content during 28 days of continuous operation. These values corresponded fully with initial laboratory-scale batch experiments, showing the successful transformation from batch to continuous processing. The obtained hydrochar from both feedstocks showed an increase in higher heating value (HHV) and a significant reduction in ash content. Pellets produced from the solids met the requirements for industrial use, demonstrating a large increase in the deformation temperature and a significant reduction in the potassium and chlorine content compared to the original feedstock. These results indicate the excellent potential of these pellets for combustion applications.

Sludges from the papermaking industry represent a challenging residue stream that is difficult to dewater using conventional processes. The successful development and scale-up of innovative processes from lab- to pilot- to industrial-scale are required to tackle challenges for waste treatment, including paper sludges. Biological paper sludge was treated via a mild hydrothermal carbonization process (TORWASH^®) to improve dewaterability of the sludge, including long-duration, continuous testing. Initial lab-scale experiments indicated the optimal treatment temperature for sludge dewatering was 190 °C. Dewaterability improved with increasing temperature, but the obtained solid yield decreased. Scaling-up to a continuous flow pilot plant required a temperature of 200 °C to achieve optimum dewatering. Pilot-scale hydrothermal treatment and dewatering resulted in solid cakes with an average dry matter content of 38% and a solid yield of 39%. This study demonstrates the benefits of hydrothermal carbonization for the dewatering of biological paper sludge without the use of dewatering aids such as fiber sludge or polyelectrolytes. The results also demonstrate the successful adaptation of a lab-scale batch process to a pilot-scale continuous flow process for hydrothermal carbonization of industrial wastewater sludge.

European aspen (Populus tremula (L.) (Salicaceae)) bark is a promising raw material in multi-step biorefinery schemes due to its wide availability and higher content of secondary metabolites in comparison to stem wood biomass. The main objective of this study was to investigate the major cell wall component-enriched fractions that were obtained from aspen bark residue after extractives isolation, primarily focusing on integration of separated lignin fractions and cellulose-enriched bark residue into complex valorization pathways. The “lignin first” biorefinery approach was applied using mild organosolv delignification. The varying solvent systems and process conditions for optimal delignification of residual aspen bark biomass were studied using a response surface methodology approach. The conditions for maximum process desirability at which the highest amount of lignin-enriched fraction was separated were as follows: 20-h treatment time at 117 °C, butanol/water 4:1 (v/v) solvent system with solid to liquid ratio of 1 to 10. At optimal separation conditions, lignin-enriched fraction exhibited a higher content of β–O–4 linkages vs. C–C linkages content in its structure as well as a high amount of hydroxyl groups, being attractive for its further valorization. At the same time, the content of glucose in products of cellulose-enriched residue hydrolysis was 52.1%, increased from 10.3% in untreated aspen bark. This indicates that this fraction is a promising raw material for obtaining cellulose and fermentable glucose. These results show that mild organosolv delignification of extracted tree bark can be proposed as a novel biorefinery approach for isolation of renewable value-added products with various application potentials.

Iridium catalysed acceptorless dehydrogenative decarbonylation of organosolv lignin is exemplified for the combined lignin defunctionalisation and liberation of synthesis gas.

Lignin holds the key for maximizing value extraction from lignocellulosic biomass. This is currently hindered by the application of fractionation methods that significantly alter the lignin structure to give highly recalcitrant materials. For this reason, it can be highly beneficial to use less severe fractionation conditions that allow for efficient extraction of lignin with retention of the β-aryl ether (β-O-4) content. Here, we present a detailed study on mild alcohol based organosolv fractionation with the aim of understanding how to achieve a balance between efficiency of lignin extraction and the structure of the resulting lignin polymers, using walnut shells as model biomass. Monitoring different extraction conditions reveals how the structure of the extracted lignin changes depending on the extraction conditions in terms of molecular weight, alcohol incorporation and H/G/S ratios. Moving from ethanol to n-pentanol it was revealed that, in particular, alcohol incorporation at the benzylic α-position of β-aryl ether units not only plays a key role in protecting the β-O-4 linking motif, but more importantly increases the solubility of larger lignin fragments under extraction conditions. This study shows that α-substitution already occurs prior to extraction and is essential for reaching improved extraction efficiencies. Furthermore, α-substitution with not only bulky secondary alcohols and tertiary alcohols, but also chloride were revealed for the first time and the latter could be involved in facilitating α-alkoxylation. Overall, this study demonstrates how by tuning the fractionation setup and conditions, the resulting lignin characteristics can be influenced and potentially tailored to suit downstream demands.

Current lignin fractionation methods use harsh conditions that alter the native lignin structure, resulting in a recalcitrant material which is undesired for downstream processing. Milder fractionation processes allow for the isolation of lignins that are high in β-aryl ether (β-O-4) content, however, at reduced extraction efficiency. The development of improved lignin extraction methods using mild conditions is therefore desired. For this reason, a flow-through setup for mild ethanosolv extraction (120 °C) was developed. The influence of acid concentration, ethanol/water ratio, and the use of other linear alcohol co-solvents on the delignification efficiency and the β-O-4 content were evaluated. With walnut shells as model feedstock, extraction efficiencies of over 55% were achieved, yielding lignin with a good structural quality in terms of β-O-4 linking motifs (typically over 60 per 100 aromatic units). For example, lignin containing 66 β-O-4 linking motifs was obtained with an 80:20 n-propanol/water ratio, 0.18 M H₂SO₄ with overall a good extraction efficiency of 57% after 5 h. The majority of the lignin was extracted in the first 2 hours and this lignin showed the best structural quality. Compared to batch extractions, both higher lignin extraction efficiency and higher β-O-4 content were obtained using the flow setup.

Lignin is an abundant natural biopolymer that has the potential to act as a renewable feedstock for valuable aromatic compounds via selective catalytic depolymerization. In recent years, elegant, mild, catalytic hydrogen neutral C-O bond cleavage methodologies have been developed on model compounds yielding acetophenone derivatives. However, none of these have been reported to be effective once applied to lignin. One of the reasons for this is the highly functionalized nature of the native lignin β-O-4 motif, which is often not taken into account in the β-O-4 model compounds used for methodology development. In this work, we demonstrate the development of a stepwise modification protocol on lignin β-O-4 model compounds to overall yield a partially defunctionalized β-O-4 motif. This was achieved by making use of an α-ethoxylated β-O-4 motif that is readily available from ethanosolv extraction of lignocellulosic biomass. This specific motif allowed us to apply selective copper catalyzed aerobic oxidation and subsequent rhodium catalyzed decarbonylation of the primary hydroxyl group in the γ position. The obtained partially defunctionalized β-O-4 lignin motif allowed effective homogeneous ruthenium catalyzed hydrogen neutral C-O bond cleavage (> 99% of 3,4-dimethoxyacetophenone and > 99% of guaiacol). The stepwise modification strategy was extended to walnut ethanosolv lignin, demonstrating that the specific structural motifs are accessible from such a readily available lignin. Overall, this work illustrates that the structure of lignin can be strategically modified to allow access to otherwise inaccessible specific aromatic compounds via selective depolymerization methodologies.