Softwood Kraft Lignin Research Articles

Self-Formation of Lignin Particles Through Melt-Extrusion for Active Biodegradable Food Packaging.

This study presents a method for the self-formation of lignin particles within a polylactic acid (PLA) matrix during melt-extrusion, eliminating the need for separation and drying steps typically associated with submicro-size lignin particles. This method effectively mitigates the problem of agglomeration often associated with the drying step. Softwood kraft lignin, guaiacyl lignin (GL-lignin), was dissolved in low-molecular-weight poly(ethylene glycol) (PEG) and was introduced into a twin-screw extruder using a liquid feeder. Lignin particles within a particle size range of 200-500 nm were observed in the extrudate of the PLA/PEG/GL-lignin composites. PLA/PEG/GL-lignin composite films were produced through blown film extrusion. These composite films demonstrated superior ultraviolet (UV)-barrier and antioxidant properties compared to neat PLA films, with optical and mechanical characteristics comparable to those of neat PLA. Moreover, migration values of the composite films in various food simulants were below regulatory limits, suggesting their potential for food packaging applications. This self-formation process offers a promising approach for utilizing lignin for PLA applications.

Solvent-Free Lignin-Silsesquioxane wood coating formulation with superhydrophobic and Flame-Retardant functionalities

There is a tremendous motivation to develop eco-friendly formulas for superhydrophobic and flame-retardant coatings. Presently used coating materials, particularly fluorinated compounds and their organic solvents, are potentially toxic. Here, we demonstrate that a silsesquioxane-grafted kraft lignin (WSL) and aluminum phosphate (AP) binder, i.e., an aqueous sustainable formula, can produce a flame retardant and superhydrophobic coating that is highly resistant to water and solvents. The chemical reaction of softwood kraft lignin (SKL) and aminopropyl/methyl silsesquioxane (WAPMSS) was studied comprehensively. NMR and XPS analyses confirmed the conversion of hydroxyl groups of SKL to Si-O-C via polycondensation. The product exhibited negligible wettability and was very hydrophobic. The dip coating of stain-grade pine wood species in the best formula containing WSL and AP dispersion (1/1 wt./wt.) rendered wood with superhydrophobic (with a water contact angle of (WCA) of 158°) and flame-retardant (with a limited oxygen index (LOI) of 27.2 %) functionalities. The exposure of coated wood to different liquids and high temperatures, as well as abrasion, touching, and knife-cutting analyses, confirmed the excellent durability of the coating formulation on wood. This paper demonstrates an eco-friendly pathway to produce a sustainable wood coating formulation with superhydrophobic and flame-retardant features.

Effect of lignin modification on the selectivity of pyrolysis products from softwood kraft lignin

The synthesis of phenol via pyrolysis of lignin can be envisaged as a prospective approach for the high-value utilization of lignin, Herein, we describe an in-depth investigation of the selective modification of lignin to effectively adjust the distribution of lignin pyrolysis products. We found that hydroxypropyl modification of lignin can facilitate the elimination of methoxy from the lignin macromolecule and improve the selectivity of phenol products. In addition, increasing the carbon number of the lignin side chains causes polymerization of pyrolysis products, which is unfavorable for the synthesis of fine chemicals via lignin pyrolysis. Conversely, an increase in lignin side-chain hydroxyl content can lead to more liquid-phase products from lignin pyrolysis, and the selectivity of phenol and its congeners will also increase. As a result, the yield of liquid products obtained via pyrolysis of lignin modified via selective oxyalkylation can reach 52 %, and the relative content of phenol and its homologs can reach 45.2 %.

Modulation of physicochemical and antioxidant properties of Pickering emulsions using colloidal lignin particles based on kraft softwood and hardwood acetone fractions

Colloidal lignin particles (CLPs) emerge as a sustainable alternative to traditional, fossil-based emulsion stabilizers. However, effectively outperforming the conventional ingredients requires addressing the challenges posed by lignin heterogeneity and structural complexity. In this study, one-step acetone fractionation was applied to softwood and hardwood kraft lignins to tackle the issue. The resulting soluble (AS) and insoluble (AI) fractions, along with the pristine lignins, underwent thorough characterization and were used to create CLPs through the hydrotropic precipitation. The acetone fraction-derived CLPs were tested for the first time as Pickering stabilizers. Notably, a strong correlation emerged between the structural traits of each lignin sample and the properties of the resulting Pickering emulsions. Such correlation allowed for a fine-tuning of their physicochemical and antioxidant features. The AS fractions, characterized by higher phenolic OH content and lower molecular weight, led to CLPs with larger sizes and reduced hydrophilic character compared to those derived from AI- and pristine lignins. The fraction-derived CLPs exhibited superior emulsifying capacity and imparted long-term stability to the formed emulsions. Moreover, the resulting Pickering emulsions showed high potential as antioxidant agents, proving their ability as multifunctional systems. Overall, this work demonstrates how the unique properties of lignin can be selectively enhanced through acetone fractionation method and seamlessly transferred to Pickering emulsions. This advancement promotes the use of lignin in high-value-added sectors such as cosmetics and personal care.

The Laccase Catalysed Tandem Lignin Depolymerisation/Polymerisation.

The development of strategies allowing either the production of high value phenolics, or the isolation of properties-enhanced materials from technical lignins represents a fundamental step in the industrial upcycling of technical lignins. Both aims are met by the strategy presented in the present work, relying on the coupling of solvent-based fractionation with the oxidative action of a new type of alkaline-stable genetically modified bacterial laccase. The described approach succeeded in the tandem, high-yield and selective isolation of valuable lignin-monomeric compounds (MCs) and high molecular weight and hydrophobicity-tailored polymerised materials (PMs) from two technical lignins, namely softwood kraft lignin (SKL), and wheat straw organosolv lignin (WSL). With respect to MCs, higher yields as compared to similar studies (up to 17.2 mg/g) were achieved. PMs from SKL samples where characterised by an almost quadrupled Mw, while in the case of WSL the Mw was approximately doubled. Noteworthy, the reaction conditions were optimized in terms of reaction temperature, time, enzymatic loading, and alkalinity for the selective production of single MCs. Most interestingly, technical lignins as well as their fractions and the PMs deriving from their laccase-catalysed oxidation showed increased hydrophobicity.

Epoxidized technical Kraft lignin as a particulate resin component for high-performance anticorrosive coatings

AbstractDeterioration of steel infrastructures is often caused by corrosive substances. In harsh conditions, the protection against corrosion is provided by high-performance coatings. The major challenge in this field is to find replacements for the fossil-based resins constituting anticorrosive coatings, due to increasing needs to synthesize new environmentally friendly materials. In this study, softwood Kraft lignin was epoxidized with the aim of obtaining a renewable resin for anticorrosive coatings. The reaction resulted in the formation of heterogeneous, solid, coarse agglomerates. Therefore, the synthetized lignin particles were mechanically ground and sieved to break up the agglomerates and obtain a fine powder. To reduce the use of fossil fuel-based epoxy novolac resins in commercial anticorrosive coatings, a series of formulations were prepared and cured on steel panels varying the content of epoxidized lignin resin. Epoxidized lignin-based coatings used in conjunction with conventional epoxy novolac resin demonstrated improved performance in terms of corrosion protection and adhesion properties, as measured by salt spray exposure and pull-off adhesion test, respectively. In addition, the importance of size fractionation for the homogeneity of the final coating formulations was highlighted. The findings from this study suggest a promising route to develop high-performing lignin-based anticorrosive coatings.

The glass transition temperature of isolated native, residual, and technical lignin

Abstract The glass transition temperatures (T g) of native, residual, and technical lignins are important to lignocellulose pulping, pulp processing and side stream utilization; however, how the structural changes from native to residual and technical lignin influences T g has proven difficult to elucidate. Since the T g of macromolecules is greatly influenced by the molecular weight, low-molecular-weight fractions, such as milled wood lignin (MWL), are poor representatives of lignin in the cell wall. To circumvent this problem, lignins of both high yield and purity were isolated from Norway spruce and softwood kraft pulp using the enzymatic mild acidolysis lignin (EMAL) protocol. Technical softwood kraft lignin was also fractionated into groups of different molecular weights, to acquire lignin that spanned over a wide molecular-weight range. A powder sample holder for dynamic mechanical analysis (DMA), was used to determine the T g of lignins, for which calorimetric methods were not sensitive enough. The T gs of EMAL were found to be closer to their in situ counterparts than MWL.

Utilizing pyrolysis cleavage products from softwood kraft lignin as a substitute for phenol in phenol-formaldehyde resins for modifying different wood species

Phenol-formaldehyde resins can be used for wood modification through an impregnation process and subsequent curing within the wood cell wall. Phenol is gained from non-renewable resources, and its substitution by renewable chemicals has been a research goal. A promising example for renewable phenol substituents are lignin-derived organic chemicals. Phenol-formaldehyde resins with such substitutions have been studied, however, knowledge of their application for wood modification is deficient. While there are attempts to modify pine and beech wood with this method, studies on other wood species are scarce. Considering the increasing use of different wood species in wood industry, determining the influence of the wood species on the modification quality is an important research goal. Therefore, in this study, vacuum-pressure impregnation of five wood species – Scots pine sapwood (Pinus sylvestris), Norway spruce (Picea abies), European beech (Fagus sylvatica), Silver birch (Betula pendula), and European aspen sapwood (Populus tremula) – with phenol-formaldehyde resins is described. Here, up to 45% of the phenol in the synthetic resin is substituted by vacuum low-temperature microwave-assisted pyrolysis cleavage products from commercial softwood kraft lignin. The solution uptake, weight% gain, leaching, and anti-swelling efficiency of the modified wood are analyzed and compared. The results indicate that up to 30% of the phenol can be substituted without significant decreases in the performance of the modification. The method gives comparable results for most of the wood species described herein, with exception of beech wood, for which the modification had a lower quality. The results could help to develop more environmentally friendly wood modification methods for several common European wood species.

Aqueous ethanol fractionation of softwood and hardwood kraft lignins: Impact on purity and properties

Industrial kraft lignins are mixtures of macromolecular components variable in both structure and composition. To maximize their value in commercial applications, they often need to be homogenized and purified. Several fractionation methods have been reported to improve the properties of kraft lignins, but these reports have been mostly limited to kraft lignins of single origins. In this study, the physicochemical properties of fractions from four industrial kraft lignins were compared. Fractionation was performed on both softwood and hardwood lignins by partial dissolution in aqueous ethanol followed by precipitation with water. The yields of each fraction varied greatly between the lignins, with differences reaching up to 35% for a single fraction. All fractions were characterized which showed that fractions having remarkably similar properties and compositions can be obtained from different lignins. Organic and inorganic impurities were found to concentrate in specific fractions which allowed the isolation of highly purified fractions of kraft lignin. These results highlight the importance of matching individual kraft lignins with suitable applications.

Structural properties of softwood lignin fractions: Revealed by NMR and Py-GC/MS

The structural complexity of industrial softwood kraft lignin (ISKL) strongly interrelates to the heterogeneous chemical reactions of kraft delignification process. In this work, structural properties of an ISKL were revealed by the investigation on the structural properties of fractions with gradient molar mass and trace/high amount of carbohydrates. Moreover, the variation in structural composition of ISKL enables its classification into three distinct categories, which potentially correspond to the the lignin dissolved at different phases of kraft delignification. In general, the low molar mass fraction, characterized by an abundance of reduced subliknages and a minimal presence of native linkages, are tentatively associated with the lignin dissovled at the inital phase of delignification. The medium molar mass fractions with trace amounts of carbohydrates, exhibiting similarities in the quantites of β-O-4, benzyl ether (BE), and β-5 linkages, are probably dissolved into kraft liquor in the period of the bulk phase of delignification. The lignin fraction with the highest molar mass, containing a large amount of native sublinkages and carbohydrates, is correlated with the lignification phase toward the late of delignification. This study of structural characteristics of lignin fractions and their relationship to kraft delignification chemistry is anticipated to facilitate the separation of lignin to fractions with significantly reduced structural heterogeneity, thereby enhancing the potential for high-value application based on their compositional structure.

Modification of plywood with phenol–formaldehyde resin: substitution of phenol by pyrolysis cleavage products of softwood kraft lignin

The modification by impregnation of veneers for the production of plywood with phenol–formaldehyde resins is a well-known method to improve the dimensional stability and fungal resistance. Because phenol is obtained from non-renewable resources, finding substitutes has been a topic of research. Due to similarities in chemical structure and availability, lignin cleavage products present a promising alternative. In this study, microwave-assisted pyrolysis cleavage products of softwood kraft lignin have been used to substitute 30% of phenol in phenol–formaldehyde resins. Scots pine veneers were impregnated with the resin, and five-layered plywoods were produced. The influence of the substitution on the bonding quality, the dimensional stability, and the leaching of resin from the specimens were studied. Mechanical properties such as the bending strength, the modulus of elasticity, as well as the dynamic impact bending strength of the plywood were analyzed. Both treatments led to plywood with good dimensional stability, and the resin was stable against leaching. The substitution of phenol with lignin cleavage products led to slightly reduced brittleness of the specimens compared to pure phenol–formaldehyde resin. This study presents a method to reduce the use of non-renewable resources, increase the use of currently underutilized lignin sources, and produce plywood with promising properties for exterior applications.

Methylation of softwood and hardwood kraft lignins with chloromethane.

Methylation is a well-established means of enhancing the thermal stability, improving the compatibility in polymer blends, and lowering the glass-transition temperature of lignins. This process normally involves reagents that are costly, associated with poor atom economy and/or highly toxic. Herein, we report the methylation of softwood and hardwood kraft lignins using chloromethane in alkaline aqueous media. This reaction proceeds in high yields at 90-110 °C under moderate pressure (40 psi) while generating environmentally benign sodium chloride and water as by-products.

Comparison of the effects of three drying methods on lignin properties

In the last few years, a serious effort has been initiated to develop standard methods for lignin characterization at the national and international levels. Thus, several Canadian and ISO standards were recently developed. The current results were generated in an effort to assist the ISO/TC6 Committee come up with a reliable standard method for the measurement of the dry solids content of lignins. In particular, this work investigated the drying of lignin using three different drying methods: conduction oven drying (105 °C), vacuum oven drying at (60 °C), and freeze drying. Ten different lignins were used in this study including wet and air-dried softwood and hardwood kraft lignins in the acid and base forms from the industrial LignoForce™ process and hydrolysis lignin from the TMP-Bio™ process. The results showed that 7 h, 48 h and 24 h were sufficient to reach a constant solids content in the case of all lignins when oven drying, vacuum oven drying under negative pressure (150 mbar), and freeze drying (25 mT) were used, respectively.Kraft lignins in the base form showed higher sensitivity to degradation compared to lignins in the acid form. The total hydroxyl group content of air-dried and wet hardwood lignins in the base form decreased by more than 50 % after vacuum oven-drying for 71.5 h or oven-drying for 16 h compared to freeze-drying for 68 h. The decrease in the total hydroxyl groups was more pronounced (70 %) when the wet softwood lignin in the base form was dried in the oven compared to freeze drying for 68 h.

Study toward a More Reliable Approach to Elucidate the Lignin Structure-Property-Performance Correlation.

The correlation between lignin structure, its properties, and performance is crucial for lignin engineering in high-value products. Currently, a widespread approach is to compare lignins which differ by more than one parameter (i.e., Kraft vs organosolv vs lignosulfonates) in various applications by attributing the changes in their properties/performance specifically to a certain variable (i.e., phenolic -OH groups). Herein, we suggest a novel approach to overcome this issue by changing only one variable at a time while keeping all others constant before investigating the lignin properties/performance. Indulin AT (Ind-AT), a softwood Kraft lignin, was chosen as the model substrate for this study. Selective (analytical) lignin modifications were used to mask/convert specific functionalities, such as aliphatic (AliphOH) including benzylic -OH (BenzOH) and phenolic -OH (PhOH) groups, carboxyl groups (-COOH) and carbonyl groups (CO) via methylation, acetylation, and reduction. The selectivity and completeness of the reactions were verified by comprehensive NMR analysis (31P and 2D HSQC) of the modified preparations together with state-of-the-art molar mass (MM) characterization. Methylene blue (MB) adsorption, antioxidant activity, and glass transition temperature (Tg) were used to demonstrate and compare the properties/performance of the obtained modified lignins. We found that the contribution of different functionalities in the adsorption of MB follows the trend BenzOH > -COOH > AlipOH > PhOH. Noteworthy, benzylic -OH contributes ca. 3 and 2.3 times more than phenolic and aliphatic -OH, respectively. An 11% and 17% increase of Tg was observed with respect to the unmodified Indulin by methylating benzylic -OH groups and through reduction, respectively, while full acetylation/methylation of aliphatic and phenolic -OH groups resulted in lower Tg. nRSI experiments revealed that phenolic -OH play a crucial role in increasing the antioxidant activity of lignin, while both aliphatic -OH groups and -COOHs possess a detrimental effect, most likely due to H-bonding. Overall, for the first time, we provide here a reliable approach for the engineering of lignin-based products in high value applications by disclosing the role of specific lignin functionalities.

Effect of demethylation of acetone-soluble softwood kraft lignin on adhesion of lignin–phenol–formaldehyde resins

Owing to the increasing interest in sustainability and bio-based materials, softwood kraft lignin (SKL) was acetone-fractionated to reduce its heterogeneity and then demethylated to substitute phenol in lignin–phenol–formaldehyde (LPF) resins to be used as bio-based wood adhesives. This study investigated the effect of the demethylation of acetone-soluble SKL (AS-SKL) on the adhesion of LPF resins, where phenol was partially replaced with acetone-soluble demethylated kraft lignin (AS-DKL). Characterization of SKL, AS-KL, and AS-DKL using gel permeation chromatography (GPC), FTIR, and 31P NMR spectroscopy showed that the demethylation was successfully performed; the molecular weight (MW) and the number of methoxy groups decreased, and the number of –OH groups increased. The MW, chemical reactions, and curing behavior of LPF resins synthesized with different AS-DKL levels (10, 20, 30, and 50 wt%) were also characterized. With the increase in AS-DKL content, the viscosity and MW of the resin increased, whereas the gelation time decreased. LPF resins with 10% AS-DKL showed the highest tensile shear strength and lowest peak curing temperature. These results suggest that 10% is an optimal AS-DKL level in LPF resins for plywood bonding and that demethylation is an effective way of utilizing SKL.

Effect of torrefaction pretreatment on the selectivity improvement of lignin pyrolysis products

Pre-regulating the molecular composition and structural characteristics of lignin before pyrolysis is of great significance for the lignin valorization. In this work, torrefaction pretreatment of softwood kraft lignin (SKL) is carried out at different temperatures, and the characterization results show that torrefaction pretreatment is beneficial for removing oxygen element from SKL, which increases the high heating value of torrefied lignins (TLs). In addition, torrefaction pretreatment has a destructive effect on Cβ-O-C4 linkages, and reduces the molecular weight of TLs. Torrefaction pretreatment also removes the thermally unstable components from SKL and increases the release rate of pyrolysis volatiles. Furthermore, torrefaction pretreatment degrades the methoxy group (-OCH3) in SKL into phenolic hydroxyl group, which reduces the yield of guaiacyl type phenols in TLs pyrolysis products, and significantly increases the yield of catechol type phenols from 23.59% in SKL to 47.50% in TL300.

Lignin Use in Enhancing the Properties of Willow Pellets

Shrub willow (Salix spp.) is an emerging lignocellulosic biomass utilized in fuel pellets as an energy source. However, improvements are needed to increase the efficacy of pellets in areas such as the energy content, durability, and hazardous carbon monoxide emissions. This study examined the effect of utilizing lignin as an additive on willow pellet properties. Two types of lignin were used in individual treatments: lignin recovered from the hot water extraction of willow (RecL) and commercial softwood kraft lignin (ComL). A statistical analysis of the ash content, energy content, bulk density, durability, pellet length, moisture absorption, and carbon monoxide emissions for the pellets with and without the addition of RecL or ComL lignin was conducted. The observed significant reduction in carbon monoxide emissions from RecL pellets was an important effect of the lignin addition. There were also significant increases in the energy content, bulk density, and durability of lignin-added pellets. While the production of carbon monoxide via pellets continues to be explored, lignin can be utilized as an additive to reduce carbon monoxide emissions and simultaneously improve other pellet properties.

Using guaiacol as a capping agent in the hydrothermal depolymerisation of kraft lignin

Abstract The depolymerisation of softwood kraft lignin was investigated, under hydrothermal conditions at 290 °C and 250 bar, with guaiacol in the reactor feed to evaluate its impact on the formation of char and on the molecular weights of the products. The effect of residence time was investigated in the time span 1–12 min. Lignin is depolymerised during the process and guaiacol is both formed and consumed during the reaction, with clearly noticeable changes as early as in the first minute of reaction. Although the addition of guaiacol in the reactor feed causes a reduction in the weight average molecular weight of the products, the yield of char increases. Longer residence times result in repolymerisation of the reaction products as well as a further increase in the yield of monoaromatic components and char.

Structure and property variations of mixed hardwood kraft lignins

Kraft lignin as an emerging renewable feedstock can be used to produce fuels, chemicals, and materials. Hardwood kraft lignin bears intrinsic variation due to wood species and the isolation process. The structure and property variation of hardwood kraft lignin could introduce new challenges and opportunities for its application. To better understand such variation, seven kraft lignin samples, originated from southern mixed hardwood (North America), northern mixed hardwood (North America), and Asian mixed hardwood, were isolated from commercial kraft pulping black liquor using both LignoBoost and LignoForce processes. Modern analytical techniques were used to elucidate the characteristics of mixed hardwood kraft lignins, including chemical composition, molecular weight, functional groups, and thermal properties. All lignin samples had a lignin content over 90% (92% to 96%) with one exception, which was northern mixed hardwood kraft lignin with 86% of lignin content and 6% polysaccharides. The elemental and methoxy analyses revealed the expected variation of hardwood kraft lignins with the methoxy content ranging from 0.85 to 1.20 per C9 unit. The weight average molecular weight exhibited a higher variation (from 4800 to 1895 Da) with a descending order of southern mixed hardwood kraft lignins, northern mixed hardwood lignins, and Asian mixed hardwood lignins. The aliphatic hydroxy groups ranged from 14 to 25 per 100 C9 units, and phenolic hydroxy groups ranged from 65 to 112 per 100 C9 units. The catecholic group content ranged from 12 to 34 per 100 C9 units, which is higher than softwood kraft lignin. The lignins isolated from the rapid displacement heating (RDH) pulping process were more condensed than from the regular kraft pulping process. 2D HSQC and quantitative 13C NMR revealed the drastic structure change upon kraft pulp with the low abundance of native lignin linkages and formation of new interunit linkages, such as stilbene, enol ethers, and 1-1’/5’. The S/G ratio was calculated using 2D HSQC spectra correcting for signal shift caused by the catecholic groups.

Single-Solvent Fractionation and Electro-Spinning Neat Softwood Kraft Lignin.

This paper reports on the production of electro-spun nanofibers from softwood Kraft lignin without the need for polymer blending and/or chemical modification. Commercially available softwood Kraft lignin was fractionated using acetone. The acetone-soluble lignin (AcSL) had an ash content of 0.06 wt %, a weight average molecular weight of 4250 g·mol-1 along with the polydispersity index of 1.73. The corresponding values for as-received lignin (ARL) were 1.20 wt %, 6000 g·mol-1, and 2.22, respectively. The AcS was dissolved in a binary solvent consisting of acetone, and dimethyl sulfoxide (2:1, v/v) was selected for dissolving the AcSL. Conventional and custom-designed grounded electrode configurations were used to produce electro-spun neat lignin fibers that were randomly oriented or highly aligned, respectively. The diameter of the electro-spun fibers ranged from 1.12 to 1.46 μm. After vacuum drying at 140 °C for 6 h to remove the solvents and oxidation at 250 °C, the fibers were carbonized at 1000, 1200, and 1500 °C for 1 h. The carbonized fibers were unfused and void-free with an average diameter of 500 nm. Raman spectroscopy, scanning electron microscopy, and image analysis were used to characterize the carbonized fibers.