Kraft Lignin Research Articles

Turning lignin into a recyclable bioresource: transesterification vitrimers from lignins modified with ethylene carbonate

Transesterification-based vitrimers from lignins modified with ethylene carbonate, to turn lignins into a recyclable aromatic bioresource.

Cationic lignin as an efficient and sustainable homogenous catalyst for aqueous Knoevenagel condensation reactions.

Knoevenagel condensation is a chemical reaction between aldehydes and active methylene-containing compounds in the presence of heterogeneous, basic homogenous organic or inorganic catalysts and solvent or neat systems. Herein, we introduced a new strategy for this synthesis by using the aqueous solution of cationic kraft lignin (CKL) as a catalyst. The CKL was synthesized through the reaction of kraft lignin (KL) with glycidyltrimethylammonium chloride (GTMAC) in a basic medium. The optimal reaction conditions for the Knoevenagel reaction were 5% catalyst load (weight of catalyst to the weight of benzaldehyde), water as the solvent, and at room temperature, which generated the products with a yield of 97%, illustrating that the CKL was an effective homogenous and green catalyst. The results confirmed that the increase in CKL charge density improved the product yield. The water-insoluble products were easily separated by filtration, and the filtrate containing the catalysts was reused effectively for 5 cycles without a significant decrease in the production yield, which would confirm the advantages of this catalyst for this reaction system. The CKL catalyst exhibited biodegradability comparable to KL. This paper discusses a novel method for Knoevenagel condensation reactions for different aldehydes in a green system utilizing a sustainable, biodegradable catalyst at room temperature and in an aqueous system.

Detection of toxic cypermethrin pesticides in drinking water by simple graphitic electrode modified with Kraft lignin@Ni@g-C3N4 nano-composite.

The detrimental effects of widespread pesticide application on the health of living organisms highlight the urgent need for technological advancements in monitoring pesticide residues at trace levels. This study involves the synthesis of a distinctive sensing material, KL@Ni@g-C3N4, which comprises nanocomposites of graphitic carbon nitride with Kraft lignin and nickel. The prepared samples were characterized using FT-IR, PXRD, TEM, SEM, and EDX techniques. The KL@Ni@g-C3N4 nanocomposite was drop-cast on a graphite electrode. Subsequently, this fabricated electrode was used to detect cypermethrin (CYP) residues in drinking water. The redox properties of the fabricated sensors were evaluated using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The limit of detection (LOD) of the fabricated sensor was determined to be 0.026 μg mL-1, which is below the maximum residual limits of CYP in the environment (0.5 μg mL-1) and within the acceptable range for food products (∼0.05 to 0.2 μg mL-1). Therefore, this study proposes a promising alternative to conventional methods for detecting pesticides in drinking water.

Phytic acid derivatized lignin as a thermally stable and flame retardant material

A phosphorus-containing flame retardant was produced via reacting phytic acid and kraft lignin in water.

Synthesis of silver nanoparticles using modified lignin as a reducing agent

The emergence and spread of microorganisms, posing a significant threat to public health globally, highlights the urgent need for sustainable solutions to combat pathogens. As a result, green synthesis has garnered increasing attention as an eco-friendly and effective approach to developing antimicrobial materials. This study explores the potential of aminated lignin as an alternative material for synthesizing silver nanoparticles, comparing its performance with commonly used kraft lignin. A one-pot green method was successfully employed to synthesize silver nanoparticles using both lignin types. By incorporating amine groups, lignin demonstrated heightened efficacy as a reducing agent, leading to a nearly fourfold increase in the concentration of silver nanoparticles. The silver nanoparticles obtained using aminated lignin displayed an average crystallite size of 50 nm and demonstrated a more uniform morphology, while those obtained using kraft lignin resulted in a smaller crystallite size of 30 nm but a broader nanoparticle size range. The concentration enhancement and improved morphology control underscore the significant impact of using aminated lignin as a reducing agent, emphasizing its potential in advanced materials synthesis. These results provide valuable insights into the utilization of amine-terminated lignin in nanoparticle synthesis and its potential in diverse applications.

Dielectric elastomers based on SEBS gel: The impact of adding kraft lignin on electro-mechanical performance

Dielectric elastomers based on SEBS gel: The impact of adding kraft lignin on electro-mechanical performance

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.

Use of Recycled Acid for Kraft Lignin Production

The present study aimed to obtain and characterize Kraft lignin from black liquor from a cellulose industry. The black liquor was collected and subjected to physical-chemical analysis. Then, acid precipitation was carried out using recycled acid from car batteries (ARA) to obtain Kraft lignin. The characterization of lignin involved techniques such as Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), dynamic light scattering ( DLS) and Zeta potential. Morphological analyzes revealed irregular structures, including plates and spherical structures. The XRD results allowed the identification of the phases present in the structure of the samples. DLS indicated variation in average sizes throughout the filtration and centrifugation process, attributed to clumping during phase separation. Zeta potential values were consistent with previous studies. The FTIR analysis highlighted characteristics of the chemical bonds of Kraft lignin, indicating the viability of the obtaining process, especially when using recycled acid, contributing to the removal of two environmentally harmful wastes: black liquor and battery acid. The lignin yield was as expected, with an average of 30.74 ± 0.0004% for PA sulfuric acid and 29.76 ± 0.0059% for recovered sulfuric acid. These results are in accordance with literature standards, especially considering the use of Eucalyptus grandis.

Study on the quality improvement of bio-oil prepared by catalytic pyrolysis of kraft lignin: the role of micropore/mesopore beta zeolites

Study on the quality improvement of bio-oil prepared by catalytic pyrolysis of kraft lignin: the role of micropore/mesopore beta zeolites

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.

Effect of Cu-modified HZSM-5 zeolites on catalytic pyrolysis of lignin to producing aromatic hydrocarbons

Lignin catalytic pyrolysis presents a promising and sustainable approach to producing aromatic molecules. Herein, we investigated the effect of modified zeolite with copper (Cu/HZSM-5) catalyst on efficiently pyrolyzed kraft lignin into aromatic hydrocarbons (AHs) production, especially mononuclear aromatic hydrocarbons (MAHs). Time-of-flight mass spectrometry (TOF-MS) was employed to compare the volatile product profiles of lignin during catalytic pyrolysis. The highest yield of MAHs reached 70.59 mg/g based on dry lignin at 550 °C, accounting for 70.23% among lignin pyrolysis products, compared to the pristine HZSM-5 zeolite catalytic system with MAHs yield of only 54.31 mg/g and of 40.34% in products. At 550 °C and 60 s residence time, the 5% Cu/HZSM-5 catalyst demonstrated the best performance compared to all other catalysts in terms of selectively producing MAHs. The results are ascribed to the enhancement of decarboxylation and aromatization processes by the doping of copper. This work demonstrates a cost-effective pathway that potentially converts kraft lignin into aromatic hydrocarbon production at a phenomenally high selectivity, providing a concept for industrial application toward biomass utilization and high value-added production.

Solar Hydrogen Production and Biomass Reforming Using Earth-Abundant Non-Toxic Si-Based Photocatalysts

The efficient production of electrochemical hydrogen and biomass refinement is crucial for the decarbonization of various industries. However, their low efficiency and high energy requirements make them impractical. In this talk, we propose using earth-abundant and non-toxic photocatalysts that can produce hydrogen and reform biomass efficiently by utilizing solar energy. Our approach involves using low bandgap Si flakes (SiF) for efficient light absorption. SiF was further modified with Ni-coordinated N-doped graphene quantum dots (Ni-NGQDs) to enable stable light-driven biomass reforming and hydrogen production. SiF/Ni-NQGDs enabled a record hydrogen productivity and concurrent vanillin production when using kraft lignin as model biomass under simulated sunlight without any buffering agent or sacrificial electron donors. SiF/Ni-NQGDs can also be easily recycled without noticeable performance degradation due to the prevention of Si deactivation through oxidation. Our findings provide valuable insights into the practical application of biomass refinement and electrochemical hydrogen production and efficient use use of solar energy.Reference)1. Y. Choi, S. Choi, I. Lee, T. V. T. Nguyen, S. Bae, J. Ryu, Y. H. Kim, S. Park, J. Ryu, Solar Biomass Reforming and Hydrogen Production with Earth-Abundant Si-Based Photocatalysts. Advanced Materials 2023, Accepted. Figure 1

Dual lignin-derived polymeric system for peptone removal from simulated wastewater

The long-term existence of peptone can breed a large number of bacteria and cause the eutrophication of municipal wastewater. Thus, removing peptone in the wastewater is a major challenge facing the current industry. This study used cationic and anionic lignin polymers, i.e., kraft lignin-[2-(methacryloyloxy)ethyl] trimethylammonium methyl sulfate (cationic lignin polymer, CLP) and kraft lignin-acrylic acid (anionic lignin polymer, ALP), as flocculants to eliminate peptone from model wastewater in the single and dual component systems. The affinity of peptone for ALP or CLP was assessed by quartz crystal microbalance with dissipation, X-ray photoelectron spectroscopy, contact angle, and vertical scan analyzer. Results illustrated that the adsorption effect of CLP for peptone was significantly superior to that of ALP owing to the stronger vital interaction between cationic polymer and peptone molecules. Based on destabilization and sedimentation analyses, introducing CLP triggered the preliminary flocculation of peptone via bridging action, as indicated by a considerable increment in the destabilization index (from 1.1 to 10.6). Moreover, peptone adsorbed more on the CLP coated surface than on the ALP coated one (14.8 vs 5.4 mg/m2), while ALP facilitated its further adsorption in the dual polymer system. This is because CLP adsorbed a part of peptone molecules on its surface. Then, ALP entrapped the unattached peptone onto the CLP coated surface through electrostatic interaction. Compared with the single polymer system, mixing ALP and CLP subsequently into the peptone solution in the dual system generated larger size aggregates (mean diameter of 6.1 μm) and made the system destabilization (Turbiscan stability index up to 58.1), thereby yielding more flocculation and sedimentation. Finally, peptone was removed successfully from simulated wastewater with a turbidity removal efficiency of 92.5%. These findings confirmed that the dual-component system containing two lignin-derived polymers with opposite charges could be viable for treating peptone wastewater.

Lignin Nanoparticles as Charge Storage Centers in Organic Battery Electrodes

Lignin, the second most abundant biopolymer on Earth, has recently emerged as a promising redox-active material for organic batteries. Different types of lignin have been explored but inherent challenges have remained, i.e., the difficulties of processing kraft lignin and the low charge storage capacity retention of lignosulfonate due to its high water-solubility. In this work, we propose the use of an alternative candidate, lignin nanoparticles (LNPs), which are insoluble, but colloidally stable dispersions in aqueous media, which, can be easily processed using different manufacturing techniques. By combining LNPs with a conducting polymer (PEDOT:PSS), we have successfully prepared a composite that has a charge storage capacity of up to 42.5 mAh/g at a current density of 1 A/g, while its capacity retention shows a good improvement (70% after 1000 cycles) in comparison to the similar systems of lignosulfonate-based electrodes. The morphology and chemical structure of LNPs are tunable, therefore, the effects of particle sizes and the preparation methods of LNPs on the electrode performance were also studied. With the obtained results, this work suggests LNPs as promising materials for the preparation of green and low-cost lignin-based energy storage devices. Keywords: Lignin nanoparticles, Organic batteries, PEDOT:PSS, Electrochemistry.

Using carboxyl groups to improve the compatibility of XNBR/lignin composites

AbstractThe paper and pulp industry produces lignin as a byproduct, which could be a bio‐based reinforcing filler for rubber. Carboxylated nitrile rubber (XNBR) contains carboxyl groups that form ionic bonds with zinc oxide, potentially increasing compatibility with lignin, compared to usual nonpolar rubbers. This study employed the traditional mixing method, two‐roll mill, to incorporate hardwood Kraft lignin without chemical or physical modification as a reinforcing filler in commercial XNBR. A mixture design of experiments was used to explore the effect on rubber/lignin interaction of the carboxyl group content (from 1% to 7% in blends of XNBR) and the amount of lignin (from 0 to 40 phr). Adding 40 phr of lignin increased stress at 100% in XNBR 7% from 1.7 to 6.3 MPa. In XNBR 1%, the increase was from 1.2 to 1.9 MPa. Lignin showed better interaction and dispersion with XNBR 7%, determined from response surface of G′ at high deformations and SEM, respectively. Loss of thermal transition in DMA indicates interaction through ionic groups. These results show that the presence of carboxyl groups enhances the rubber/lignin interaction. This research open possibilities of compatibilization of lignin, offering guidance for future studies and technologies involving lignin in technical applications.Highlights Lignin dispersion increased as the carboxyl group content increased to 7% (w/w). Stress at 100% elongation increased 370% with 40 phr of lignin and 7% carboxyl. Rubber/lignin interaction as per G′ increased with carboxyl groups. Loss of thermal transition suggests lignin/carboxy/zinc oxide interaction. Lignin can be used as a reinforcing filler in nitrile carboxylated rubber.

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.

Industrial Kraft Lignin Based Binary Cathode Interface Layer Enables Enhanced Stability in High Efficiency Organic Solar Cells.

Herein, a binary cathode interface layer (CIL) strategy based on the industrial solvent fractionated LignoBoost kraft lignin (KL) is adopted for fabrication of organic solar cells (OSCs). The uniformly distributed phenol moieties in KL enable it to easily form hydrogen bonds with commonly used CIL materials, i.e., bathocuproine (BCP) and PFN-Br, resulting in binary CILs with tunable work function (WF). This work shows that the binary CILs work well in OSCs with large KL ratio compatibility, exhibiting equivalent or even higher efficiency to the traditional CILs in state of art OSCs. In addition, the combination of KL and BCP significantly enhanced OSC stability, owing to KL blocking the reaction between BCP and nonfullerene acceptors (NFAs). This work provides a simple and effective way to achieve high-efficient OSCs with better stability and sustainability by using wood-based materials.

Potential of hardwood kraft lignin as a bio-based dye for cotton fabrics

The dyeing characteristics of hardwood kraft lignin (KL) were investigated on cotton fabrics, assessing its potential as a sustainable and environmentally friendly dye. Dyeability was evaluated by varying the KL concentrations, temperature, and time. An aqueous solution of Na2CO3 (1.0%) as the dye bath and a fabric-to-liquor ratio of 1:50 were used. Cationizing effects were studied using (3-chloro-2-hydroxypropyl) trimethylammonium chloride (CHPTAC), and the mordanting effects of various mordants were also evaluated. Post-mordanting was performed with FeSO4, FeCl2, Fe-lactate (Fe-lac), MgSO4, CuCl2, CuSO4, and Al2(SO4)3. A mordant concentration of 1 mM o.w.f. (0.5 mM for Al2(SO4)3), with a liquor ratio of 1:30, at 60 °C for 30 min were employed. Suitable dyeing conditions were 2.0% o.w.b., 90 °C, and 90 min, resulting in a brownish color of the cotton fabric. The fabrics exhibited a range of light brown to light grayish brown colors and showed lighter colors than the untreated fabrics when mordanted with MgSO4 and Al2(SO4)3. The color difference (ΔE) between cationized and uncationized cotton fabrics was 3.48. From the colorfastness assessment, KL-dyed cotton fabric showed good rubbing and washing fastness for staining, but poor light and washing fastness for fading.

Lignin/PVA hydrogel with enhanced structural stability for cationic dye removal

In this study, a lignin-based hydrogel for wastewater treatment was prepared by incorporating kraft lignin (KL) into a poly (vinyl alcohol) (PVA) matrix. The underwater structural stability of the KL-PVA hydrogel was guaranteed through physicochemical crosslinking, involving freeze–thaw process and chemical crosslinking reaction. The KL-PVA hydrogel displayed superior compressive characteristics compared to the original PVA hydrogel. This improvement was attributed to the chemical crosslinking and the reinforcing effect of the incorporated KL microparticles. The incorporation of anionic KL microparticles into the PVA three-dimensional network structure enhanced the cationic methylene blue (MB) and crystal violet (CV) adsorption efficiency of the prepared KL-PVA hydrogel. The MB adsorption results were well explained by pseudo-2nd order kinetics model and Langmuir isotherm model. Electrostatic forces, hydrogen bonding and π-π stacking interactions were the main adsorption mechanisms between cationic dyes and KL surfaces, indicating the potential of KL-PVA hydrogel as an effective adsorption material. Moreover, regulating the molecular weight of PVA not only prevented lignin leakage from the KL-PVA hydrogel but also elevated the KL content within the hydrogel, consequently improving its dye removal performance. For KL-PVA hydrogel with high molecular weight PVA, the MB and CV adsorption capacities were 193.8 mg/g and 190.0 mg/g, respectively.

Influence of char‐forming lignin in combination with aluminium phosphinate on thermal stability and combustion properties of polyamide 11 blends

AbstractPolyamide 11 (PA) blends based on char‐forming industrial lignin and aluminum phosphinate (AlP) were prepared to improve flame retardant (FR) properties using a green and eco‐friendly approach. This study investigates the thermal degradation and combustion behavior of PA blends prepared by using AlP in combination with two different types of industrial lignins (i.e., kraft lignin (DL) and lignosulphonate lignin (LL). Thermogravimetric (TG) analysis showed that ternary blends containing LL and AlP developed higher char residue up to 10.7 wt% upon decomposition in inert atmospheres. The combination of lignin and AlP increases the thermal stability by shifting the initial decomposition temperature (T5%) and temperature at maximum decomposition (Tmax) to a higher temperature range, attributed to the stabilization of decomposition products. Furthermore, combustion behavior studied by cone calorimeter (forced combustion) and pyrolysis combustion flow calorimeter (PCFC) tests presented a significant reduction in the peak of heat release rate (PHRR) and total heat release (THR). It was found that LL and AlP‐containing blends more effectively decreased fire parameters like PHRR and THR than that of DL and AlP‐containing blends. The best interaction with reduced fire‐retardant properties was obtained when 10 wt% loading of lignin (DL/LL) and AlP was used. The reduction in heat release parameters was mainly ascribed to the condensed phase mechanism by forming an efficient protective char layer, which acts as a barrier against heat and mass transfer between the condensed and the gas phases. Raman spectroscopy analysis also confirmed the formation of the protective graphitic layer in the condensed phase.