Search

Ternary deep eutectic solvents (DESs) are gaining increased attention to serve as a cheap green alternative medium for the processing of lignocellulosic biomass. For example, mixtures of choline chloride (ChCl), ethylene glycol (EG), and oxalic acid (OA) were recently explored for the fractionation of lignocellulosic biomass into its main components. Interestingly, during this processing, the recovered lignin was structurally modified by incorporation of EG, which altered its solubility properties and led to the need for different lignin recovery strategies. This offers an excellent starting point for a deeper investigation of the effect of acidic DES systems on the structure of lignin. In particular, native-like residual enzyme lignins (RELs) that are hard to completely dissolve in organic solvents are specifically suitable for this task. Here, a ternary DES is used consisting of ChCl/EG with OA or trifluoromethanesulfonic acid (HOTf) as a third component. The results showed that both solvent systems led to high EG incorporation into REL. The HOTf system showed a lesser extent of lignin depolymerization at similar modification levels as it already induced modification at lower temperature (25-30 °C). Low recovery yields from typical acidic precipitation were observed for treatment with both acidic DES systems. Analysis of THF and DCM extracts showed that the products in the water phase included small EG modified lignin fragments and aromatic monomers released from lignin aryl ether linkage cleavage. This analysis details the types of other products that can be expected and where these will end up during fractionation. These results show that the treatment of lignin with acidic DES in the presence of alcohols leads to low- and high-molecular-weight products that are not effectively recovered by typical precipitation procedures.

Modified starches are used widely in the food industry but often have a low nutritional value, lacking minerals vital for the human body, such as magnesium. Magnesium addition to native starches has been shown to result in changes in pasting properties. However, little work has been done on the addition of magnesium and other divalent cations to highly oxidised starches. In this work, we used dibasic magnesium hypochlorite (DMH) to oxidise potato starch to an industrially relevant degree of oxidation while at the same time introducing magnesium into the starch structure. We found that magnesium incorporation changes the pasting properties of starch and increases the gelatinisation temperature significantly, possibly due to an ionic cross-linking effect. These properties resemble the properties found for heat-moisture-treated potato starches. This change in properties was found to be reversible by performing a straightforward exchange of metal cations, either from sodium to magnesium or from magnesium to sodium. We show in this work the potential of the addition of divalent cations to highly oxidised starches in modifying the rheological and pasting properties of these starches and at the same time adding possible health benefits to modified starches by introducing magnesium.

Combining solid acid catalysts with enzyme reactions in aqueous environments is challenging because either very acidic conditions inactivate the enzymes, or the solid acid catalyst is neutralized. In this study, Amberlyst-15 encapsulated in polydimethylsiloxane (Amb-15@PDMS) is used to deprotect the lignin depolymerization product G-C2 dioxolane phenol in a buffered system at pH 6.0. This reaction is directly coupled with the biocatalytic reduction of the released homovanillin to homovanillyl alcohol by recombinant horse liver alcohol dehydrogenase, which is subsequently acylated by the promiscuous acyltransferase/hydrolase PestE_I208A_L209F_N288A in a one-pot system. The deprotection catalyzed with Amb-15@PDMS attains up to 97 % conversion. Overall, this cascade enables conversions of up to 57 %. ispartof: Chemsuschem vol:16 issue:10 ispartof: location:Germany status: Published online

The precise elucidation of native lignin structures plays a vital role for the development of “lignin first” strategies such as reductive catalytic fractionation. The structure of lignin and composition of the starting material has a major impact on the product yield and distribution. Here, the differences in structure of lignin from birch, pine, reed, and walnut shell were investigated by combining detailed analysis of the whole cell wall material, residual enzyme lignin, and milled wood lignin. The results of the 2D heteronuclear single quantum coherence NMR analysis could be correlated to the product from Ru/C-catalyzed hydrogenolysis if monomeric products from ferulate and p-coumaryl and its analogous units were also appropriately considered. Notably, residual polysaccharide constituents seemed to influence the selectivity towards hydroxy-containing monomers. The results reinforced the importance of adequate structural characterization and compositional analysis of the starting materials as well as distinct (dis)advantages of specific types of structural characterization and isolation methods for guiding valorization potential of different biomass feedstocks.

Oxidized starch can be efficiently prepared using H2O2 as an oxidant and iron(III) tetrasulfophthalocyanine (FePcS) as a catalyst, with properties in the same range as those for commercial oxidized starches prepared using NaOCl. Herein, we performed an in-depth study on the oxidation of potato starch focusing on the mode of operation of this green catalytic system and its fate as the reaction progresses. At optimum batch reaction conditions (H2O2/FePcS molar ratio of 6000, 50 °C, and pH 10), a high product yield (91 wt %) was obtained with substantial degrees of substitution (DSCOOH of 1.4 and DSCO of 4.1 per 100 AGU) and significantly reduced viscosity (197 mPa·s) by dosing H2O2. Model compound studies showed limited activity of the catalyst for C6 oxidation, indicating that carboxylic acid incorporation likely results from C-C bond cleavage events. The influence of the process conditions on the stability of the FePcS catalyst was studied using UV-vis and Raman spectroscopic techniques, revealing that both increased H2O2 concentration and temperature promote the irreversible degradation of the FePcS catalyst at high pH. The rate and extent of FePcS degradation were found to strongly depend on the initial H2O2 concentration where also the rapid decomposition of H2O2 by FePcS occurs. These results explain why the slow addition of H2O2 in combination with low FePcS catalyst concentration is beneficial for the efficient application in starch oxidation.

5-Hydroxy-2-methylfurfural (HMF) has a high derivatization potential and is considered the sleeping giant of biobased platform chemicals. It is accessible by the acid hydrolysis of various carbohydrate-containing feeds, preferably those high in fructose content. We here report a detailed study on the use of thick juice, an intermediate sucrose (SUC)-rich stream in a sugar factory, and pure SUC for the synthesis of HMF in a batch reactor setup [in the presence of water and sulfuric acid (0.01 M) and at 180 °C]. Distinct differences in reactivity were found for both feeds, related to the presence of impurities (i.e., organic acids and salts) in the thick juice. To better understand the effect of the thick juice impurities, detailed model studies were performed involving the use of a model solution of SUC spiked with one of the thick juice impurities (organic acids such as maleic acid and a range of salts with potassium, sodium, calcium, and magnesium as the cations and carbonates, chlorides, and sulfates as the anions). The data were successfully modeled using a kinetic model for the main reactions in the network. The developed model revealed that sulfate anions have a major effect on the HMF yield and the batch time required to reach its optimum and are the likely cause of the differences in reactivity between pure SUC and thick juice.

The global increase in lignocellulosic ethanol production goes in tandem with an increase in lignin-rich stillage that remains underutilized to date. Anaerobic digestion could valorize residual (biodegradable) organic fractions into biogas, leaving a lignin-rich digested stillage (LRDS). This LRDS from the lignocellulosic ethanol production has been assessed as a feedstock for slow and fast pyrolysis in earlier studies, with the intention to increase the overall output of useful products or energy carriers from the starting material. While using this lignin-rich feedstock, ex situ catalytic vapor-phase upgrading (VPU) of fast pyrolysis vapors with fractional condensation was conducted over Na/ZSM-5, H/ZSM-5, and Fe/ZSM-5 catalysts. Semicontinuous fast pyrolysis experiments have been carried out at a reaction temperature of 480 degrees C in a mechanically stirred sand bed, which was connected directly to a fixed bed of catalyst particles for ex situ upgrading of the fast pyrolysis vapors. The carbon and mass yields in heavy phase liquids decreased after catalytic VPU (mass: ca. 8-11 wt %; carbon: ca. 11-15 wt %), compared to noncatalytic pyrolysis (mass: ca. 18 wt %; carbon: ca. 23 wt %). However, the yield in specific compounds, that is, alkylphenols and aromatics such as BTX, increased much upon catalytic VPU (especially for Fe/ZSM-5). For Fe/ZSM-5, the concentration in alkylphenols and aromatics was 20.8 wt % on liquid basis and the yield was 1.7 wt % on as-received (a.r.) feedstock basis. For noncatalytic pyrolysis, the concentration in alkylphenols and aromatics was 2.1 wt % (liquid basis) with a yield of 0.4 wt % (a.r. feedstock basis). This study thus demonstrates the potential of (modified) catalysts to upgrade lignin pyrolysis vapors.

A mild lignin-first acidolysis process (140 °C, 40 min) was developed using the benign solvent dimethyl carbonate (DMC) and ethylene glycol (EG) as a stabilization agent/solvent to produce a high yield of aromatic monophenols directly from softwood lignocellulose (pine, spruce, cedar, and Douglas fir) with a depolymerization efficiency of 77-98 %. Under the optimized conditions (140 °C, 40 min, 400 wt % EG and 2 wt % H2 SO4 to pinewood), up to 9 wt % of the aromatic monophenol was produced, reaching a degree of delignification in pinewood of 77 %. Cellulose was also preserved, as evidenced by a 85 % glucose yield after enzymatic digestion. An in-depth analysis of the depolymerization oil was conducted by using GC-MS, HPLC, 2 D-NMR, and size-exclusion chromatography, which provided structural insights into lignin-derived dimers and oligomers and the composition of the sugars and derived molecules. Mass balance evaluation was performed.

The development of fundamentally new valorization strategies for lignin plays a vital role in unlocking the true potential of lignocellulosic biomass as sustainable and economically compatible renewable carbon feedstock. In particular, new catalytic modification and depolymerization strategies are required. Progress in this field, past and future, relies for a large part on the application of synthetic model compounds that reduce the complexity of working with the lignin biopolymer. This aids the development of catalytic methodologies and in‐depth mechanistic studies and guides structural characterization studies in the lignin field. However, due to the volume of literature and the piecemeal publication of methodology, the choice of suitable lignin model compounds is far from straight forward, especially for those outside the field and lacking a background in organic synthesis. For example, in catalytic depolymerization studies, a balance between synthetic effort and fidelity compared to the actual lignin of interest needs to be found. In this Review, we provide a broad overview of the model compounds available to study the chemistry of the main native linking motifs typically found in lignins from woody biomass, the synthetic routes and effort required to access them, and discuss to what extent these represent actual lignin structures. This overview can aid researchers in their selection of the most suitable lignin model systems for the development of emerging lignin modification and depolymerization technologies, maximizing their chances of successfully developing novel lignin valorization strategies., Model me right: A review of lignin model compounds for the most abundant linking motifs is provided as well as the state‐of‐the‐art approaches for their synthesis. A framework is also offered for researches working in the field of lignin valorization on what considerations to take into account when choosing the right model for the right stage of methodological development to get the most out of every model compound study.

Lignocellulose, as the most abundant type of inedible biomass, is considered as a promising renewable feedstock for making fuels, chemicals, and materials. However, its complex structure makes most of current biorefinery processes suffer from low resource utilization rates, high energy consumption or ill-defined market orientation of the obtained products. Here, we propose and evaluate the EXA (Ethanol, Xylose, Adhesive) biorefinery strategy based on current xylose industry. This process integrates four conversion and separation stages to consecutively produce ethanol, xylose, and adhesive with total carbon utilization of 79.6%. The key innovation is the establishment of an easy-to-operate process for direct production of high-quality adhesive from a lignin-rich liquid fraction that makes the overall process significantly more sustainable. Techno-economic analysis (TEA) shows that the revenue of proposed EXA process increases more than 110 times compares with the current process and life cycle assessment (LCA) demonstrates a much lower CO2 footprint from an environmental burden per unit of revenue perspective.

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 beta-O-4 motif; which is often not taken into account in the beta-O-4 model compounds used for methodology development. In this work, we demonstrate the development of a stepwise modification protocol on lignin beta-O-4 model compounds to overall yield a partially defunctionalized beta-O-4 motif. This was achieved by making use of an a-ethoxylated beta-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 y position. The obtained partially defunctionalized beta-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.

A new, sustainable catalytic route for the synthesis of tetrahydrofuran-2,5-dicarboxylic acid (THFDCA), a compound with potential application in polymer industry, is presented starting from the bio-based platform chemical 5-(hydroxymethyl)furfural (HMF). This conversion was successfully achieved via oxidation of tetrahydrofuran-2,5-dimethanol (THFDM) over hydrotalcite (HT)-supported gold nano-particle catalysts (similar to 2 wt %) in water. THFDM was readily obtained with high yield (>99%) from HMF at a demonstrated 20 g scale by catalytic hydrogenation. The highest yield of THFDCA (91%) was achieved after 7 h at 110 degrees C under 30 bar air pressure and without addition of a homogeneous base. Additionally, Au-Cu bimetallic catalysts supported on HT were prepared and showed enhanced activity at lower temperature compared to the monometallic gold catalysts. In addition to THFDCA, the intermediate oxidation product with one alcohol and one carboxylic acid group (5-hydroxymethyl tetrahydrofuran-2-carboxylic acid, THFCA) was identified and isolated from the reactions. Further investigations indicated that the gold nanoparticle size and basicity of HT supports significantly influence the performance of the catalyst and that sintering of gold nanoparticles was the main pathway for catalyst deactivation. Operation in a continuous setup using one of the Au-Cu catalysts revealed that product adsorption and deposition also contributes to a decrease in catalyst performance.

Pyrolytic lignin is the collective name of the lignin-derived fraction of pyrolysis liquids. Conversion of this fraction to biobased chemicals is considered an attractive valorization route. Here we report experimental studies on the ozonation of a pine-derived pyrolytic lignin dissolved in methanol (33 wt %). Results show a high reactivity of ozone, and a molecular weight reduction of up to 40% was obtained under mild conditions (0 °C, atmospheric pressure) without the need for catalysts. Detailed analysis of the product mixtures (GC/MS-FID, HPLC, GPC, NMR) showed the presence of low molecular weight (di)acids and esters, along with larger highly oxygenated aliphatics. A reaction network is proposed including the heterolytic cleavage of aromatic rings, followed by secondary reactions. The observations were supported by experimental studies using representative pyrolytic lignin model compounds and a biosynthetic lignin oligomer, which aided further elucidation on the reactivity trends for different chemical functionalities. Accordingly, the presence of hydroxy and methoxy substituents on the aromatic rings is shown to be the main reason for the high reactivity of pyrolytic lignin upon ozone exposure.

Kraft lignin is an abundantly available side product from the pulp and paper industry. It has a complex aromatic structure and has great potential to serve as a feedstock for renewable aromatic chemicals. In this communication, we show that a simple mechanochemical pretreatment (viz., ball milling) of commercial Indulin AT kraft lignin before solvent-free hydrotreatment results in a 15% increase in the recovered oil yield with 15% more alkylphenols and a 33% reduction in solids compared to the unmilled sample. This increase raises the carbon efficiency toward the oil based on elemental composition from 76 to 91%, respectively. This enhanced catalytic performance is attributed to improved heat transfer and allowing for better contact between the kraft lignin particles of reduced size and the catalyst particles, prompting enhanced depolymerization at an earlier stage of the reaction, thereby preventing charring.

Acidolysis in conjunction with stabilization of reactive intermediates has emerged as one of the most powerful methods of lignin depolymerization that leads to high aromatic monomer yields. In particular, stabilization of reactive aldehydes using ethylene glycol results in the selective formation of the corresponding cyclic acetals (1,3-dioxolane derivatives) from model compounds, lignin, and even from softwood lignocellulose. Given the high practical utility of this method for future biorefineries, a deeper understanding of the method is desired. Here, we aim to elucidate key mechanistic questions utilizing a combination of experimental and multilevel computational approaches. The multiscale computational protocol used, based on ReaxFF molecular dynamics, represents a realistic scenario, where a typical experimental setup can be reproduced confidently given the explicit molecules of the solute, catalyst, and reagent. The nudged elastic band (NEB) approach allowed us to characterize the key intermolecular interactions involved in the reaction paths leading to crucial intermediates and products. The high level of detail obtained clearly revealed for the first time the unique role of sulfuric acid as a proton donor and acceptor in lignin β-O-4 acidolysis as well as the reaction pathways for ethylene glycol stabilization, and the difference in reactivity between compounds with different methoxy substituents., Multiscale computational modeling reveal the role of sulfuric acid and ethylene glycol in the selective breakdown of lignin.

C.S.L. thanks the Leverhulme Trust Early Career Fellowship (ECF-2018-480). Z.W. acknowledges the China Scholarship Council for funding (grant number 201706300138). 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 was 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. Publisher PDF

Fast pyrolysis is an efficient technology to convert lignocellulosic biomass to a liquid product. However, the high contents of oxygenated compounds and water hinder the direct utilization of pyrolysis oils. Here, we report an upgrading concept to obtain liquid products with improved product properties and enriched in valuable low molecular weight chemicals and particularly alkylphenols. It entails two steps, viz. i) pyrolysis with in-situ staged condensation at multiple kg scale followed by ii) a catalytic hydrotreatment of selected fractions using a Ru/C catalyst. Of all pyrolysis oil fractions after staged condensation, the product collected in a condenser equipped with an electrostatic precipitator (ESP) at 120 °C was identified as the most attractive for hydrotreatment when considering product yields and composition. The best hydrotreatment results (Ru/C, 350 °C, 100 bar H2, 4 h) were achieved using beechwood and walnut shells as feedstock, resulting in a high oil yield (about 64 wt% based on pyrolysis oil fraction intake) with a higher heating value of about 37 MJ/kg and enriched in alkylphenols (about 16 wt%). Overall, it was shown that the type of biomass (beech sawdust, walnut granulates, and pine/spruce sawdust) has a limited impact on liquid and alkylphenols yields which implies feedstock flexibility of this integrated concept.

5-Hydroxymethylfurfural (HMF) is a platform chemical that can be produced from renewable carbohydrate sources. HMF can be converted to 1,2,4-benzenetriol (BTO) which after catalytic hydrodeoxygenation provides a route to cyclohexanone and cyclohexanol. This mixture, known as KA oil, is an important feedstock for polymeric products such as nylons which use benzene as feedstock that is obtained from the BTX fraction produced in oil refineries. Therefore, the conversion of HMF to BTO provides a renewable, alternative route toward products such as nylons. However, BTO is usually considered an undesired byproduct in HMF synthesis and is only obtained in small amounts. Here, we show that Lewis acid catalysts can be utilized for the selective conversion of HMF to BTO in subsuper critical water. Overall, up to 54 mol % yield of BTO was achieved at 89% HMF conversion using ZnCl2. ZnCl2 and similarly effective Zn(OTf)2 and Fe(OTf)2 are known as relatively soft Lewis acids. Other Lewis acid like Hf(OTf)4 and Sc(OTf)3 gave increased selectivity toward levulinic acid (up to 33 mol %) instead of BTO, a well-known HMF derivative typically obtained by acid catalysis. Catalytic hydrodeoxygenation of BTO toward cyclohexanone in water was achieved in up to 45% yield using 5 wt % Pd on Al2O3 combined with AlCl3 or Al(OTf)3 as catalysts. Additionally, a mild selective oxygen induced dimerization pathway of BTO to 2,2′,4,4′,5,5′-hexahydroxybiphenyl (5,5′-BTO dimer) was identified., A Lewis acidic metal salt catalyzed pathway to 1,2,4-benzenetriol in water, a new catalytic route to access biobased C6-aromatics.

Biobased furanics like 5-hydroxymethylfurfural (5-HMF) are interesting platform chemicals for the synthesis of biofuel additives and polymer precursors. 5-HMF is typically prepared from C6 ketoses like fructose, psicose, sorbose and tagatose. A known byproduct is 2-hydroxyacetylfuran (2-HAF), particularly when using sorbose and psicose as the reactants. We here report an experimental and kinetic modeling study on the rate of decomposition of 2-HAF in a typical reaction medium for 5-HMF synthesis (water, Brönsted acid), with the incentive to gain insights in the stability of 2-HAF. A total of 12 experiments were performed (batch setup) in water with sulfuric acid as the catalyst (100–170 °C, CH2SO4 ranging between 0.033 and 1.37 M and an initial 2-HAF concentration between 0.04 and 0.26 M). Analysis of the reaction mixtures showed a multitude of products, of which levulinic acid (LA) and formic acid (FA) were the most prominent (Ymax,FA = 24 mol %, Ymax,LA = 10 mol %) when using HCl. In contrast, both LA and FA were formed in minor amounts when using H2SO4 as the catalyst. The decomposition reaction of 2-HAF using sulfuric acid was successfully modeled (R2 = 0.9957) using a first-order approach in 2-HAF and acid. The activation energy was found to be 98.7 (±2.2) kJ mol–1., An experimental and kinetic modeling study on the rate of decomposition of 2-hydroxyacetylfuran in water using a Brönsted acid was investigated in a batch setup.

Lignin is a promising feedstock for the replacement of conventional carbon sources for the production of chemicals and fuels. In this paper, results are reported for the depolymerization of various residual lignins in the absence of a catalyst by utilizing ozone. Reactions were performed in a microreactor setup ensuring high gas-liquid mass transfer rates, a low inventory of ozone, and straightforward scale-up possibilities. The ozonation is demonstrated using a representative model compound (vanillin) and various lignins (pyrolytic and organosolv) dissolved in methanol (2.5 wt %). Experiments were performed under ambient conditions, at gas-liquid flow ratios ranging from 30 to 90 and short residence times on the order of 12-24 s. Analyses of the products after methanol removal revealed the presence of (di)carboxylic acids, methyl esters, and acetals. Extensive depolymerization was achieved (i.e., up to 30% for pyrolytic lignin and 70% for organosolv lignins). Furthermore, a two-step approach in which the ozonated lignin is further hydrotreated (350-400 degrees C, 100 bar H-2, 4 h, Pd/C as catalyst) showed a substantial increase in depolymerization efficiency, yielding a 2.5-fold increased monomer yield in the product oil compared to a hydrotreatment step only.

The pyrolysis of lignocellulosic biomass generates a liquid product, known as pyrolysis oil, that can be further processed into biofuels and value-added chemicals. During pyrolysis, cellulose and hemicelulose fractions are converted into a range of water-soluble sugar derivatives, for which several valorisation strategies exist. On the other hand, lignin is broken down into so-called pyrolytic lignin, a water-insoluble complex mixture of aromatic oligomers that requires different upgrading strategies than the sugar rich fraction. Here, we report an experimental study on the valorisation of pyrolytic lignin via catalytic hydrotreatment in the absence of an external solvent. A variety of carbon-supported noble-metal heterogeneous catalysts were tested (Ru/C, Pd/C, Pt/C and Rh/C), as well as conventional hydrotreatment catalysts (sulphided NiMo/Al 2 O 3 and CoMo/Al 2 O 3 ) to obtain valuable low molecular weight aromatic and phenolic compounds. Overall, depolymerized liquids were obtained with organic yields of up to 63 wt%. Pd/C was shown to be the best catalyst, yielding 59 wt% of monomers based on the organic product (i.e. 33 wt% based on pyrolytic lignin intake). While noble metal catalysts favored higher monomer yields, though with some over-reduction of aromatic rings to saturated hydrocarbons, sulphided catalysts were more efficient in deoxygenation and aromatization reactions, but yielded less monomers. The hydrocracking efficiency was shown to be strongly dependent on the reaction temperature. Based on the experimental data, a global reaction network is proposed. The high monomer yields reveal the potential of catalytic hydrotreatment for the upgrading of pyrolytic lignin into valuable phenolics and aromatics.

In the Supporting Information of the original article (https://pubs.acs.org/doi/10.1021/acssuschemeng.0c08901), the x-axes in Figures S6c and d are wrongly labeled. It is stated that the reaction times are in “minutes”; however, the reaction times are actually in hours. Additionally, for Figure S6d, the indicated times are incorrect. A new Supporting Information file is provided here in which these mistakes have been corrected.

Kraft lignin, a side-product of the paper industry, is considered an attractive feedstock for the production of biorenewable chemicals. However, its recalcitrant nature and sulfur content render catalytic conversions challenging. This study demonstrates the efficacy of noble metal-based catalysts for the production of a lignin oil enriched in alkylphenolic and aromatic compounds, by a catalytic hydrotreatment of Kraft lignin without the use of an external solvent. Eight commercially available catalysts were evaluated using four different metals (Ru, Pt, Pd, Rh) on two supports (activated carbon and Al2O3). The product oils were extensively analyzed by means of GPC, GCxGC-FID, GC-MS-FID, and elemental analysis. The catalysts were characterized by various techniques (N-2 physisorption, NH3-TPD, XRD and TEM) before and after reaction, and their physico-chemical properties were correlated with catalytic performance. Al2O3 as support gave better results than carbon as support in terms of lignin oil yield and composition, due to a combination of higher total acidity, mildly acidic sites and a mesoporous structure. The metallic phase also significantly affected product distribution. The best results were obtained using a Rh/Al2O3 catalyst, resulting in a lignin oil yield of 36.3 wt% on a lignin intake and a total monomer yield of 30.0 wt% on lignin intake including 15.3 wt% of alkylphenolic and 7.9 wt% of aromatic compounds, and with a sulfur content

This work was funded by the European Union (Marie Curie ITN ‘SuBiCat’ PITN-GA-2013-607044, PJD, CWL, NJW, PCKL, KB, JGdeV) as well as EP/J018139/1, EP/K00445X/1 grants (NJW and PCJK) and an EPSRC Doctoral Prize Fellowship (CSL). The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields, under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy to handle metal triflates (M(OTf)x). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol, or methyl aromatics obtained by catalytic decarbonylation. Notably, when the former method was ultimately tested on lignin, especially Fe(OTf)3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield. Postprint

Lignin valorization strategies are a key factor for achieving more economically competitive biorefineries based on lignocellulosic biomass. Most of the emerging elegant procedures to obtain specific aromatic products rely on the lignin substrate having a high content of the readily cleavable β-O-4 linkage as present in the native lignin structure. This provides a miss-match with typical technical lignins that are highly degraded and therefore are low in β-O-4 linkages. Therefore, the extraction yields, and the quality of the obtained lignin are of utmost importance to access new lignin valorization pathways. In this manuscript, a simple protocol is presented to obtain lignins with high β-O-4 content by relatively mild ethanol extraction that can be applied to different lignocellulose sources. Furthermore, analysis procedures to determine the quality of the lignins are presented together with a depolymerization protocol that yields specific phenolic 2-arylmethyl-1,3-dioxolanes, which can be used to evaluate the obtained lignins. The presented results demonstrate the link between lignin quality and potential for the lignins to be depolymerized into specific monomeric aromatic chemicals. Overall, the extraction and depolymerization demonstrates a trade-off between the lignin extraction yield and the retention of the native aryl-ether structure and thus the potential of the lignin to be used as the substrate for the production of chemicals for higher-value applications.