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The demand for high-performance bio-based materials towards achieving more sustainable manufacturing and circular economy models is growing significantly. Kraft lignin (KL) is an abundant and highly functional aromatic/phenolic biopolymer, being the main side product of the pulp and paper industry, as well as of the more recent 2nd generation biorefineries. In this study, KL was incorporated into a glassy epoxy system based on the diglycidyl ether of bisphenol A (DGEBA) and an amine curing agent (Jeffamine D-230), being utilized as partial replacement of the curing agent and the DGEBA prepolymer or as a reactive additive. A D-230 replacement by pristine (unmodified) KL of up to 14 wt.% was achieved while KL–epoxy composites with up to 30 wt.% KL exhibited similar thermo-mechanical properties and substantially enhanced antioxidant properties compared to the neat epoxy polymer. Additionally, the effect of the KL particle size was investigated. Ball-milled kraft lignin (BMKL, 10 μm) and nano-lignin (NLH, 220 nm) were, respectively, obtained after ball milling and ultrasonication and were studied as additives in the same epoxy system. Significantly improved dispersion and thermo-mechanical properties were obtained, mainly with nano-lignin, which exhibited fully transparent lignin–epoxy composites with higher tensile strength, storage modulus and glass transition temperature, even at 30 wt.% loadings. Lastly, KL lignin was glycidylized (GKL) and utilized as a bio-based epoxy prepolymer, achieving up to 38 wt.% replacement of fossil-based DGEBA. The GKL composites exhibited improved thermo-mechanical properties and transparency. All lignins were extensively characterized using NMR, TGA, GPC, and DLS techniques to correlate and justify the epoxy polymer characterization results. [ABSTRACT FROM AUTHOR]

Sub‐micro organosolv lignin (OBs) isolated from beechwood biomass, comprising of sub‐micro sized particles (570 nm) with low molecular weight and dispersity and relatively high total phenolic −OH content, is utilized for the production of bio‐based epoxy polymer composites. OBs lignin is incorporated into the glassy epoxy system based on diglycidyl ether of bisphenol A (DGEBA) and aliphatic polyoxypropylene α,ω‐diamine (Jeffamine D‐230), being utilized both as a curing agent, partially replacing D‐230, and as an additive, substituting part of both petroleum‐derived components. Up to 12 wt % replacement of D‐230 by OBs lignin is achieved, whereas approximately 17 wt % of OBs effectively replaces the conventional epoxy polymer. The incorporation of OBs lignin in the polymeric matrix is achieved without the use of any solvent or previous functionalization. Enhanced properties are obtained, with substantial increases in tensile strength, strain, stiffness, glass transition temperature, antioxidant activity, and resistance to solvents. [ABSTRACT FROM AUTHOR]

Textile effluents pose a massive threat to the aquatic environment, so, sustainable approaches for environmentally friendly multifunctional remediation methods degradation are still a challenge. In this study, composites consisting of bismuth oxyhalide nanoparticles, specifically bismuth oxychloride (BiOCl) nanoplatelets, and lignin-based biochar were synthesized following a one-step hydrolysis synthesis. The simultaneous photocatalytic and adsorptive remediation efficiency of the Biochar–BiOCl composites were studied for the removal of a benchmark azo anionic dye, methyl orange dye (MO). The influence of various parameters (such as catalyst dosage, initial dye concentration, and pH) on the photo-assisted removal was carried out and optimized using the Box–Behnken Design of RSM. The physicochemical properties of the nanomaterials were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, thermogravimetric analysis, nitrogen sorption, and UV–Vis diffuse reflectance spectroscopy (DRS). The maximum dye removal was observed at a catalyst dosage of 1.39 g/L, an initial dye concentration of 41.8 mg/L, and a pH of 3.15. The experiment performed under optimized conditions resulted in 100% degradation of the MO after 60 min of light exposure. The incorporation of activated biochar had a positive impact on the photocatalytic performance of the BiOCl photocatalyst for removing the MO due to favorable changes in the surface morphology, optical absorption, and specific surface area and hence the dispersion of the photo-active nanoparticles leading to more photocatalytic active sites. This study is within the frames of the design and development of green-oriented nanomaterials of low cost for advanced (waste)water treatment applications. [ABSTRACT FROM AUTHOR]

Lignin, being one of the main structural components of lignocellulosic biomass, is considered the most abundant natural source of phenolics and aromatics. Efforts for its valorisation were recently explored as it is mostly treated as waste from heat/energy production via combustion. Among them, polymer-based lignin composites are a promising approach to both valorise lignin and to fine tune the properties of polymers. In this work, organosolv lignin, from beech wood, was used as fillers in a poly (lactic acid) (PLA) matrix. The PLA/lignin composites were prepared using melt mixing of masterbatches with neat PLA in three different lignin contents: 0.5, 1.0 and 2.5 wt%. Lignin was used as-isolated, via the organosolv biomass pretreatment/fractionation process and after 8 h of ball milling. The composites were characterised with Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy, X-ray Diffraction (XRD), and Differential Scanning Calorimetry (DSC). Additionally, their antioxidant activity was assessed with the 2,2-Diphenyil-1-picrylhydrazyl (DPPH) method, the colour was measured with a colorimeter and the mechanical properties were evaluated with tensile testing. Ball milling, at least under the conditions applied in this study, did not induce a further substantial decrease in the already relatively small organosolv lignin primary particles of ~1 μm. All the produced PLA/lignin composites had a uniform dispersion of lignin. Compression-moulded films were successfully prepared, and they were coloured brown, with ball-milled lignin, giving a slightly lighter colour in comparison with the as-received lignin. Hydrogen bonding was detected between the components of the composites, and crystallization of the PLA was suppressed by both lignin, with the suppression being less pronounced by the ball-milled lignin. All composites showed a significantly improved antioxidant activity, and their mechanical properties were maintained for filler content 1 wt%. [ABSTRACT FROM AUTHOR]

The main objective of this study was to investigate the characteristic properties of lignin-modified bitumen with different lignin contents. The first step was the characterization of the physicochemical and thermal properties of the kraft lignin powder along with the determination of its microstructure. This was achieved by carrying out an elemental analysis, Gel Permeation Chromatography (GPC), Thermogravimetric Analysis (TGA)/Derivative Thermogravimetry (DTG), Fourier Transformation Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Dynamic Light Scattering (DLS) and Confocal Microscopy. After the latter tests, three (3) blends with different lignin contents (5%, 10% and 15% by weight of bitumen) were produced. Characteristic properties such as penetration, softening point, elastic recovery, force ductility, dynamic viscosity and storage stability were determined for the reference bitumen and the three lignin blends. The main conclusion was that kraft lignin powder hardens the conventional bitumen. Specifically, the addition of 15% lignin to the bitumen hardened the blend to such a degree that the bitumen changed category from 50/70 to 35/50 with respect to EN 12591. [ABSTRACT FROM AUTHOR]

Acetone and ethanol extraction of lignin deposits from the surface of hydrothermally (liquid hot water) pretreated beech wood biomass alleviates the lignin inhibitory effects during enzymatic hydrolysis of cellulose to glucose and boosts the enzymatic digestibility to high values (≈70 %). Characterization of the extracted lignins (FTIR, pyrolysis/GC–MS, differential thermogravimetry, gel permeation chromatography) indicated high purity, low molecular weight, and features that suggest that it consists mainly of fragments of the native wood lignin partially depolymerized and recondensed on the biomass surface during the hydrothermal pretreatment. The pyrolysis products of the extracted surface lignins suggest their high potential as a feedstock for the production of high added value phenolic compounds. When the enzymatic hydrolysis of the pretreated and extracted biomass solids was assisted by mild wet milling, near complete cellulose digestibility (≥95 %) could be achieved. In the context of the biorefinery and whole‐biomass valorization concept, it was also shown that the hydrothermally (hemicellulose‐deficient) pretreated and delignified biomass solids could be also successfully used for the production of crude cellulase from Trichoderma reesei cultures, providing a simple and low‐cost method for the complementary production of cellulases by utilizing fractions of the integrated hydrolysis process. Boosting biomass enzymatic digestibility: Acetone and ethanol extraction of lignin deposits from the surface of hydrothermally (liquid hot water) pretreated beech wood biomass alleviates the lignin inhibitory effects during enzymatic hydrolysis of cellulose to glucose and boosts the enzymatic digestibility to high values (≈70 %). [ABSTRACT FROM AUTHOR]

This paper presents a techno-economic analysis (TEA) of six (6) scenarios of the kraft lignin catalytic (CFP) and thermal (TFP) fast pyrolysis towards the production of high value-added chemicals (HVACs) and electric energy, based on experimental data from our previous work. ASPEN PLUS was used to simulate the proposed plants/scenarios and retrofitted custom-based economic models that were developed in Microsoft EXCEL. The results showed that scenarios 1 and 2 in which the produced bio-oil is used as fuel for electricity production are the most cost-deficient. On the other hand, scenarios 3 and 6 that utilize the light bio-oil fraction to recover distinct HVACs, along with the use of heavier fractions for electricity production, have showed a significant investment viability, since profitability measures are high. Furthermore, scenarios 4 and 5 that refer to the recovery of mixtures (fractions) of HVACs, are considered an intermediate investment option due to the reduced cost of separation. All the proposed scenarios have a substantial total capital investment (TCI) which ranges from 135 MM€ (scenario 4) to 380 MM€ (scenario 6) with a Lang factor of 6.08, which shows that the CAPEX results are within reason. As far as the comparison of lignin CFP and TFP goes, it is shown that lignin CFP leads to the production of aromatic and phenolic monomers which have a substantial market value, while TFP can lead to important value-added chemicals with a lower OPEX than CFP. A target of return of investment (ROI) of 32% has been set for the selling prices of the HVACs. In summary, this study aims at listing and assessing a set of economic indicators for industrial size plants that use lignin CFP and TFP towards the production of high value-added chemicals and energy production and to provide simulation data for comparative analysis of three bio-oil separation methods, i.e. distillation, liquid-liquid extraction and moving bed chromatography. [Display omitted] • Lignin thermal and catalytic pyrolysis define the basis for the techno-economic screening. • Chromatography, extraction and distillation separation methods are assessed. • Options of co-production of value-added chemicals and electricity are investigated. • Investment on HVACs products leads to significantly reduced pay out times. • Increased CAPEX and OPEX for the moving bed chromatography separation method. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomass is an abundant renewable source of chemicals and fuels. Lignin, one of biomass main structural components being widely available as by-product in the pulp and paper industry and in the process of second generation bioethanol, can provide phenolic and aromatic compounds that can be utilized for the manufacture of a wide variety of polymers, fuels, and other high added value products. The effective depolymerisation of lignin into its primary building blocks remains a challenge with regard to conversion degree and monomers selectivity and stability. This review article focuses on the state of the art in the liquid phase reductive depolymerisation of lignin under relatively mild conditions via catalytic hydrogenolysis/hydrogenation reactions, discussing the effect of lignin type/origin, hydrogen donor solvents, and related transfer hydrogenation or reforming pathways, catalysts, and reaction conditions. [ABSTRACT FROM AUTHOR]

Bifunctional catalysts based on nickel supported on ZSM-5 and BETA zeolites were studied in the hydrodeoxygenation of lignin derived model compounds as well as in surrogate mixtures simulating the light fraction of lignin fast pyrolysis bio-oil. A screening of the hydrodeoxygenation reaction conditions (temperature, time, H 2 pressure, catalyst amount) was carried out using the simplest phenolic compound, phenol. As in real lignin bio-oils more complex phenolic compounds are present, a series of relevant alkyl- and methoxy-substituted phenol and benzene (o- and m-cresol, catechol, anisole, guaiacol, syringol, creosol and 1,2,3-trimethoxybenzene) were also investigated as feedstocks. Furthermore, the effect of the different porous and acidic properties of the zeolitic supports was investigated in the hydrodeoxygenation of guaiacol. The conversion of the model phenolics and the yield of the respective (alkyl)cyclohexanes at relatively mild conditions (220 °C, 50 bar H 2 , 1 h) were in the range of 80–100% and 47–83%, respectively, being dependent mainly on the complexity/side-chain group of the phenolic/benzylic ring and on the balanced content of Brønsted acid sites of increased strength. Regarding the hydrodeoxygenation of the surrogate mixture (C 7 -C 10 phenolics), 100% hydrodeoxygenation efficiency was achieved towards >60% yield of (alkyl)cyclohexanes (C 6 -C 9 hydrocarbons). All hydrodeoxygenation tests were conducted in hexadecane as solvent/substrate in order to simulate model co-processing (i.e. bio-based phenolics with petroleum derived feedstocks) conditions. Reusability tests revealed the stability of the catalysts which showed partial (30%) deactivation after the third catalytic cycle. [Display omitted] • Bifunctional nickel supported zeolites catalysts successfully catalyzed HDO of phenolics to cycloalkanes. • Hydrodeoxygenation is strongly influenced by the structural complexity of the phenolic compound. • Porous properties, number and strength of acid sites oz zeolitic can control the process. • Catalysts were active in the HDO of surrogate mixture simulating light fraction of lignin pyrolysis oil. • Catalyst can be reused up to (at least) three successive catalytic cycles. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lignin valorization process superstructure optimized by mathematical modelling. • Performances of different biorefineries were assessed based on the type of technical lignin. • Phenol-formaldehyde resins revealed the highest costs and yields. • Vanillin production was a profitable option to valorize lignin. • Aromatic monomers can be an opportunity when their market price exceed 2.00€/kg. Lignin, the most abundant aromatic biopolymer on Earth, is often considered a biorefinery by-product, despite its potential to be valorized into high-added-value chemicals and fuels. In this work, an integrated superstructure-based optimization model was set up and optimized using mixed-integer non-linear programming for the conversion of technical lignin to three main biobased products: aromatic monomers, phenol–formaldehyde resins, and aromatic aldehydes/acids. Several alternative conversion pathways were simultaneously compared to assess the profitability of lignins-based processes by predicting the performance of technologies with different TRL. Upon employing key technologies such as hydrothermal liquefaction, dissolution in solvent, or high-temperature electrolysis, the technical lignins could have a market value of 200 €/t when the market price for aromatic monomers, resins, and vanillin is at least 2.0, 0.8, and 15.0 €/kg, respectively. When lower product selling prices were considered, the aromatic monomers and the resins were not profitable as target products. [ABSTRACT FROM AUTHOR]