Search Results (25)

The depolymerization of lignin represents a promising strategy for its efficient utilization as a precursor for industrial raw materials. However, achieving both high efficiency and environmental sustainability remains a significant challenge. In this study, we present an aqueous electrochemical approach employing nickel as an electrocatalyst, enabling both depolymerization and partial de-aromatization of Kraft lignin under mild reaction conditions. Using an aqueous sodium carbonate medium, room temperature and ambient pressure, we achieved lignin depolymerization over reaction times ranging from 5 to 20 h. Characterization by nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of aliphatic products such as acetate and formate, while high-resolution mass spectrometry (HRMS) confirmed the formation of a wide range of phenolic compounds. The conversion of lignin into valuable aromatic and aliphatic compounds offers a promising pathway for the synthesis of a wide range of organic chemicals and their subsequent industrial utilization, thereby supporting the development of a more sustainable economy. Full article

Lignin, a complex aromatic biopolymer abundant as waste in biorefineries and the pulp and paper industry, holds significant potential for valorization. This study presents the oxidative depolymerization of Lignoboost lignin (LB) using H₂O₂ under mild, solvent- and catalyst-free, inherently acidic conditions at 50–70 °C. The process aimed to produce functionalized low-molecular-weight oligomers, retaining aromaticity, and aliphatic dicarboxylic acids, rather than complete monomerization. The depolymerized LB was rich in aromatic dimers-trimers (68.6 wt.%) with high functionalization (2.75 mmol/g OHphen, 3.58 mmol/g OHcarb, 19.5 wt.% of H in -CH=CH-), and aliphatic dicarboxylic acids (53.4 wt.% of monomers). Acidic conditions provided higher depolymerization and functionalization than alkaline, alongside simplified product recovery. The process was also successfully applied to Kraft lignin, demonstrating versatility and robustness even with higher polymeric content feedstocks. The optimized conditions were scaled up (×25), improving efficiency and yielding Mw 464 g/mol and Đ 1.3. As proof of concept, the scaled-up product underwent radical crosslinking, resulting in a new biopolymer with higher thermal stability than LB (54.2 wt.% residual mass at 600 °C versus 36.1 wt.%). This green, scalable process enhances lignin valorization by producing functionalized low-molecular-weight lignin oligomers and dicarboxylic acids that can be used independently or together to form crosslinked networks. Full article

Lignin is considered a renewable source for the production of valuable aromatic chemicals and liquid fuel. Solvent depolymerization of lignin is a fruitful strategy for the valorization of lignin. However, Kraft lignin is highly prone to produce char (a by-product) during the hydrothermal depolymerization process due to its poor solubility in organic solvents. Therefore, the minimization of char formation remains challenging. The purpose of the present study was to fractionate Kraft lignin in methanol to obtain low-molecular-weight fractions that could be further depolymerized in supercritical methanol to produce aromatic monomers and to suppress char formation. The results showed that the use of methanol-soluble lignin achieved a bio-oil yield of 45.04% and a char yield of 39.6% at 280 °C for 2 h compared to 28.57% and 57.73%, respectively, when using raw Kraft lignin. Elemental analysis revealed a high heating value of 30.13 MJ kg⁻¹ and a sulfur content of only 0.09% for the bio-oil derived from methanol-soluble lignin. The methanol extraction process reduced the oxygen content and increased the hydrogen and carbon contents in the modified lignin and bio-oil, indicating that the extracted lignin fraction had an enhanced deoxygenation capability and a higher energy content. These findings highlight the potential of methanol-soluble Kraft lignin as a valuable resource for sustainable energy production and the production of aromatic compounds. Full article

Driven by the urgent need for sustainable alternatives to fossil fuels, the focus on the exploration of lignocellulosic biomass, particularly lignin, as a promising renewable feedstock for biofuels and high-value chemicals has intensified. This study investigated the depolymerization of KL using a DES comprising ChCl and ZnCl₂. Our analysis systematically focused on the effects of reaction temperature, time, and the DES-to-lignin ratio on the yields and characteristics of the products. Optimal KL depolymerization was observed at a temperature of 190 °C and a duration of 8 h, yielding a maximum liquid product yield of 54.44% and RL yield of 45.56%. The results revealed that increasing the reaction temperature enhanced the depolymerization process owing to a reduction in the viscosity of the DES, which improved mass transfer and interactions with lignin. Under these optimal conditions, the molecular weight of the bio-oil was considerably lower (M_w = 1498 g/mol and M_n = 1061 g/mol) than that of the bio-oil obtained without DES treatment (M_w = 1872 g/mol and M_n = 1259 g/mol), indicating a more favorable molecular weight distribution with DES treatment. Furthermore, elemental analysis revealed a reduction in the O, N, and S contents of the RL following DES treatment, increasing the high heating value from 24.82 MJ kg⁻¹ for the non-DES-treated RL to 26.44 MJ kg⁻¹ for the DES-treated RL. These findings underscore the potential of the (ChCl:ZnCl₂) DES as a sustainable and effective medium for lignin valorization, paving the way for the synthesis of high-quality biofuels and chemicals from lignocellulosic biomass. Full article

The catalytic oxidation of phenethoxybenzene as a lignin model compound with a β-O-4 bond was conducted using the Keggin-type polyoxometalate nanocatalyst (TBA)₅[PMo₁₀V₂O₄₀]. The optimization of the process’s operational conditions was carried out using response surface methodology. The statistically significant variables in the process were determined using a fractional factorial design. Based on this selection, a central circumscribed composite experimental design was used to maximize the phenethoxybenzene conversion, varying temperature, reaction time, and catalyst load. The optimal conditions that maximized the phenethoxybenzene conversion were 137 °C, 3.5 h, and 200 mg of catalyst. In addition, under the optimized conditions, the Kraft lignin catalytic depolymerization was carried out to validate the effectiveness of the process. The depolymerization degree was assessed by gel permeation chromatography from which a significant decrease in the molar mass distribution Mw from 7.34 kDa to 1.97 kDa and a reduction in the polydispersity index PDI from 6 to 3 were observed. Furthermore, the successful cleavage of the β-O-4 bond in the Kraft lignin was verified by gas chromatography–mass spectrometry analysis of the reaction products. These results offer a sustainable alternative to efficiently converting lignin into valuable products. Full article

Producing polyhydroxyalkanoate (PHA) from lignin through biological conversion has great further potential, but is held by its high heterogeneous characteristic toxicity of the depolymerized products, and low bioconversion of the depolymerized products. In this study, a Fenton-like reaction, which is inspired by fungal decay strategy, was reported to cleave Kraft lignin linkages and produce low toxic mono-aromatic and low molecular organic compounds for microbial conversion. The treatment improved the bioconversion of lignin to PHA by 141.7% compared to Kraft lignin. The bond cleavage of Kraft lignin was characterized by Py-GC/MS and 2D NMR. Seven major depolymerized products were chosen to test their toxicity effect on bacterial fermentation. Furthermore, 920.4 mg of PHA was obtained from 1-L black liquor after Fenton-like reaction treatment. This is a novel attempt mimicking fungal decay strategy coupled with the microbial conversion of lignin into high-value PHA with a sustainable future. Full article

Here, we report work on developing an enzymatic process to improve the functionalities of industrial lignin. A kraft lignin sample prepared from marine pine was treated with the high-redox-potential laccase from the basidiomycete fungus Pycnoporus cinnabarinus at three different concentrations and pH conditions, and with and without the chemical mediator 1-hydroxybenzotriazole (HBT). Laccase activity was tested in the presence and absence of kraft lignin. The optimum pH of PciLac was initially 4.0 in the presence and absence of lignin, but at incubation times over 6 h, higher activities were found at pH 4.5 in the presence of lignin. Structural changes in lignin were investigated by Fourier-transform infrared spectroscopy (FTIR) with differential scanning calorimetry (DSC), and solvent-extractable fractions were analyzed using high-performance size-exclusion chromatography (HPSEC) and gas chromatography–mass spectrometry (GC–MS). The FTIR spectral data were analyzed with two successive multivariate series using principal component analysis (PCA) and ANOVA statistical analysis to identify the best conditions for the largest range of chemical modifications. DSC combined with modulated DSC (MDSC) revealed that the greatest effect on glass transition temperature (Tg) was obtained at 130 U g cm⁻¹ and pH 4.5, with the laccase alone or combined with HBT. HPSEC data suggested that the laccase treatments led to concomitant phenomena of oligomerization and depolymerization, and GC–MS revealed that the reactivity of the extractable phenolic monomers depended on the conditions tested. This study demonstrates that P. cinnabarinus laccase can be used to modify marine pine kraft lignin, and that the set of analytical methods implemented here provides a valuable tool for screening enzymatic treatment conditions. Full article

Lignin is a raw material that can potentially be converted into valuable compounds through depolymerization reactions in addition to its use as a polymer or material. However, the chemical recalcitrance and the heterogeneous composition and structure of lignin make it challenging to establish processes that add value to this complex aromatic biopolymer. In this work, solvent fractionation was applied to obtain lignin fractions with a narrowed molecular weight and specific structural characteristics, improving its homogeneity and purity. A kraft lignin was submitted to fractionation using different ratios of acetone, ranging from 60 to 15% v/v, in aqueous mixtures. The composition, structure, and molecular weight of each fraction were studied and their potential applications were evaluated. The most water-soluble fraction has more phenolic OH, less aliphatic OH groups, and shows the lowest content of aryl-ether linkages, which is in accordance with its highest degree of condensation. On the other hand, the insoluble fraction from the mixture with 60% of acetone has the lowest molecular weight and the highest content of inorganic material. Radar plots were applied for lignin fractions evaluation and the fraction with the highest potential (IF 30:70) was submitted to alkaline oxidation with O₂. The results were compared with the products yielded from kraft lignin. An increase of about 13 and 19% was found for vanillin and syringaldehyde, respectively, when the fraction IF 30:70 was submitted to oxidation. In conclusion, the proposed fractionation process showed to be an effective method to obtain lignin fractions with specific composition and structural characteristics that could improve its potential as a source of high added-value monomeric phenolic compounds. Full article

The usage of laccases is a sustainable and environmentally friendly approach to modifying the Kraft lignin structure for use in certain applications. However, the inherent structure of Kraft lignin, as well as that resulting from laccase modification, still presents challenges for fundamental comprehension and successful lignin valorization. In this study, bacterial and fungal laccases were employed to modify eucalypt Kraft lignin. To evaluate the type and range of the chemical and structural changes of laccase-treated lignins, different NMR techniques, including solution ¹H and 2D NMR (heteronuclear single quantum correlation (HSQC)), and solid-state ¹³C NMR, were applied. Size exclusion chromatography and infrared spectroscopy were also used. Interestingly, HSQC analysis showed substantial changes in the oxygenated aliphatic region of lignins, showing an almost complete absence of signals corresponding to side-chains due to laccase depolymerization. Simultaneously, a significant loss of aromatic signals was observed by HSQC and ¹H NMR, which was attributed to a deprotonation of the lignin benzenic rings due to polymerization/condensation by laccase reactions. Then, condensed structures, such as α-5′, 5-5′, and 4-O-5′, were detected by HSQC and ¹³C NMR, supporting the increment in molecular weight, as well as the phenolic content reduction determined in lignins. Full article

Kraft lignin was treated with subcritical water at moderate temperatures (120–220 °C) in different gas atmospheres, with the goal of optimizing its depolymerization under mild conditions. Lignin depolymerization was observed and compared using different homogeneous and heterogeneous catalysts in both nitrogen and carbon dioxide atmospheres. The most important treatment parameters for maximum lignin depolymerization and the highest yields of phenolic and other aromatic monomers were optimized. The influence of the process temperature, pressure, and time in both gas atmospheres was defined and optimized for maximum liberation of monomers into the aqueous phase. The yields of total phenols and other aromatics in the nitrogen atmosphere were the highest at 150 °C, whereas treatment in the carbon dioxide atmosphere required higher temperatures (200 °C) for a comparable efficiency. The effects of phenol addition as a capping agent in lignin depolymerization were observed and defined for both gas atmospheres. Phenol addition caused a remarkable increase in the total phenols content in the aqueous phase; however, it did not significantly affect the contents of other aromatics. The antioxidant properties of lignin hydrolysates obtained at different temperatures in different gas atmospheres were compared, correlated with the total phenols contents, and discussed, showing the promising potential of lignin hydrolysates obtained under mild subcritical water conditions. Full article

The solvent effect in the catalytic depolymerization of the three-dimensional network of lignin is discussed based on recent reports in this field. Also, the results of an experimental study on the depolymerization of kraft lignin are presented. The cleavage of ether bonds within the lignin network was promoted using ruthenium and platinum on activated carbon (Ru/C and Pt/C), two common hydrogenolysis catalysts. Methanol was identified as a suitable solvent. Noteworthy, under the chosen reaction conditions, the catalysts showed significant resilience to the sulfur present in kraft lignin. The conversion of kraft lignin to lignin oil was strongly affected by the reaction conditions. Although the Ru/C catalyst provided the highest yield at supercritical conditions, a maximum yield was obtained for the Pt/C catalyst at near-critical conditions. The formation of guaiacol, 4-alkylguaiacols, isoeugenol, and 4-ethyl-2,6-dimethoxyphenol is attributed to the solubility of oligomeric lignin fragments in the solvent and the relative propensity of specific groups to adsorb on the catalyst surface. Full article

Being the major renewable source of bio-aromatics, lignin possesses considerable potential for the chemical industry as raw material. Kraft lignin is a couple product of paper industry with an annual production of 55,000,000 ton/y and is considered the largest share of available lignin. Here we report a facile approach of Kraft lignin depolymerization to defined oligomeric units with yields of up to 70 wt.%. The process implies utilization of an aqueous base in combination with a metal containing catalyst and an alcohol under non-oxidative atmosphere at 300 °C. An advantage of the developed approach is the facile separation of the oligomer product that precipitates from the reaction mixture. In addition, the process proceeds without char formation; both factors make it attractive for industrialization. The suppression of the repolymerization processes that lead to char formation is possible when the combination of metal containing catalyst in the presence of an alcohol is used. It was found that the oligomer units have structural features found in phenol-acetaldehyde resins. These features result from the base catalyzed condensation of lignin fragments with in situ formed aldehydes. Catalytic dehydrogenation of the alcohol provides the latter. This reaction pathway is confirmed by the presence condensation products of Guerbet type reactions. Full article

Lignin is one of the main components of lignocellulosic biomass and corresponds to the first renewable source of aromatic compounds. It is obtained as a by-product in 100 million tons per year, mainly from the paper industry, from which only 2–3% is upgraded for chemistry purposes, with the rest being used as an energy source. The richness of the functional groups in lignin makes it an attractive precursor for a wide variety of aromatic compounds. With this aim, we investigated the Pd-catalyzed depolymerization of lignin under mild oxidizing conditions (air, 150 °C, and aqueous NaOH) producing oxygenated aromatic compounds, such as vanillin, vanillic acid, and acetovanillone. Palladium catalysts were implemented following different strategies, involving nanoparticles stabilized in water, and nanoparticles were supported on TiO₂. Significant conversion of lignin was observed in all cases; however, depending on the catalyst nature and the synthetic methods, differences were observed in terms of selectivity in aromatic monomers, mainly vanillin. All these aspects are discussed in detail in this report, which also provides new insights into the role that Pd-catalysts can play for the lignin depolymerization mechanism. Full article

One-pot deoxygenation of kraft lignin to aromatics and hydrocarbons of fuel-range quality is a promising way to improve its added value. Since most of the commercially resourced kraft lignins are impure (Na, S, K, Ca, etc., present as impurities), the effect of these impurities on the deoxygenation activity of a catalyst is critical and was scrutinized in this study using a NiMoS/Al₂O₃ catalyst. The removal of impurities from the lignin indicated that they obstructed the depolymerization. In addition, they deposited on the catalyst during depolymerization, of which the major element was the alkali metal Na which existed in kraft lignin as Na₂S and single-site ionic Na⁺. Conditional experiments have shown that at lower loadings of impurities on the catalyst, their promotor effect was prevalent, and at their higher loadings, a poisoning effect. The number of moles of impurities, their strength, and the synergism among the impurity elements on the catalyst were the major critical factors responsible for the catalyst’s deactivation. The promotor effects of deposited impurities on the catalyst, however, could counteract the negative effects of impurities on the depolymerization. Full article

Valorization of industrial low-value side-streams are of great interest, contributing to boosts in the circular economy. In this context, lignin side-streams of the pulp and paper industry were oxypropylated to produce biobased polyols and tested in the synthesis of rigid polyurethane (RPU) foams. E. globulus lignins, namely a lignin isolated from an industrial Kraft black liquor and depolymerized lignins obtained as by-products of an oxidation process, were used. RPU foams, synthesized with 100% lignin-based polyols and using a 1.1 NCO/OH ratio, were characterized concerning apparent density, morphology, thermal conductivity, thermal stability, and heat release rate (HRR). Foams containing the lignin-based polyols presented densities varying from 44.7 to 112.2 kg/m³ and thermal conductivity in the range of 37.2–49.0 mW/mK. For the reference foam (sample produced with 100% wt. Daltofoam TP 32015 polyol), values of 70.9 kg/m³ and 41.1 mW/mK were obtained, respectively. The achieved results point out the viability of using the generated lignin-based polyols at 100% content in RPU foams, mainly when depolymerized lignins are used. Moreover, fire retardancy was favored when the lignin-based polyols were introduced. The proposed strategies can contribute to establishing the integrated pulp and paper biorefinery concept where material synthesis (polyols and RPU foams) can be combined with chemical production (vanillin and syringaldehyde). Full article