Properties of Bark Particleboard Bonded with Demethylated Lignin Adhesives Derived from Leucaena leucocephala Bark

Lignin extraction from bark can maximize the utilization of biomass waste,offer cost-effectiveness,and promote environmental friendliness when employed as an adhesive material in bark particleboard production.Particles of fine(0.2 to 1.0 mm),medium(1.0 to 2.5 mm),and coarse(2.5 to 12.0 mm)sizes,derived from the bark of Leucaena leucocephala,were hot-pressed using a heating plate at 175℃for 7 min to create single-layer particleboards measuring 320 mm×320 mm×10 mm,targeting a density of 700 kg/m^(3).Subsequently,the samples were trimmed and conditioned at 20℃and 65%relative humidity.In this study,we compared bark particleboard bonded with urea formaldehyde(UF)adhesive to fine-sized particleboard bonded with demethylated lignin adhesive.The results indicated that bark particleboards utilizing demethylated lignin and UF adhesives exhibited similar qualities.Coarse particleboard showed differences in modulus of elasticity(MOE)and modulus of rupture(MOR),while medium-sized particles exhibited significant variations in moisture content(MC)and water absorption(WA).Furthermore,the thickness swelling of coarse and medium-sized particles under wet and oven-dried conditions exhibited notable distinctions.Overall,the demethylated lignin adhesive extracted from L.leucocephala bark demonstrated similar quality to UF adhesive,with particle size correlating inversely to the strength of the bark particleboard.

Green synthesis of ZSM-5 using silica fume and catalytic co-cracking of lignin and plastics for production of monocyclic aromatics

ZSM-5 with hierarchical pore structure was synthesized by a simple two-step hydrothermal crystallization from silica fume without using any organic ammonium templates.The synthesized ZSM-5 were oval shaped particles with a particle size about 2.0 μm and weak acid-dominated with proper Brønsted(B)and Lewis(L)acid sites.The ZSM-5 was used for catalytic co-cracking of n-octane and guaiacol,lowdensity polyethylene(LDPE)and alkali lignin(AL)to enhance the production of benzene,toluene,ethylbenzene and xylene(BTEX).The most significant synergistic effect occurred at n-octane/guaiacol at 1:1 and LDPE/AL at 1:3,under the condition,the achieved BTEX selectivity were 24%and 33%(mass)higher than the calculated values(weighted average).The highest BTEX selectivity reached 88.5%,which was 3.7%and 54.2%higher than those from individual cracking LDPE and AL.The synthesized ZSM-5 exhibited superior catalytic performance compared to the commercial ZSM-5,indicating potential application prospect.

Thermo-Mechanical, Physico-Chemical, Morphological, and Fire Characteristics of Eco-Friendly Particleboard Manufactured with Phosphorylated Lignin Addition

Lignin,lignosulfonate,and synthesized phosphorylated lignosulfonate were introduced as greenfillers in citric acid-sucrose adhesives for bonding particleboard fabricated from areca leaf sheath(ALS).The characteristics of particleboards were compared to that of ultralow emitting formaldehyde(ULEF-UF).Thefillers derived from Eucalyptus spp.kraft-lignin were added forflame retardancy enhancement.10%of each lignin and modified lig-nin was added into the ULEF-UF and citric acid-sucrose bonded particleboards.Analyses applied to particle-boards included thermal characteristics,X-ray diffraction analysis(XRD),morphological properties,Fourier transform infrared spectroscopy(FTIR),as well as physical,mechanical,andfire resistance characteristics of the laboratory-fabricated particleboards.Lignin and modified lignin resulted in improved thermal stability of the composites bonded with ULEF-UF while the improvement in the particleboard bonded with citric acid-sucrose was not significant.The introduction offiller exerted a higher influence on the UF-bonded particleboards compared to composites fabricated with citric acid-sucrose.Generally,the presence of lignin,lignosulfonate,and phosphorylated lignosulfonate enhanced the mechanical strength of the ULEF-bonded particleboards,although their dimensional stability has deteriorated.Markedly,the use of lignin and lignosulfonate enhanced thefire resis-tance of the particleboards produced with lower observed weight loss.All laboratory particleboards exhibited satisfactoryfire resistance,attaining a V-0 rating in according to the UL-94 standard.

Late sowing enhances lodging resistance of wheat plants by improving the biosynthesis and accumulation of lignin and cellulose

Delayed sowing mitigates lodging in wheat. However, the mechanism underlying the enhanced lodging resistance in wheat has yet to be fully elucidated. Field experiments were conducted to investigate the effects of sowing date on lignin and cellulose metabolism, stem morphological characteristics, lodging resistance, and grain yield. Seeds of Tainong 18,a winter wheat variety, were sown on October 8(normal sowing) and October 22(late sowing) during both of the 2015–2016 and 2016–2017 growing seasons. The results showed that late sowing enhanced the lodging resistance of wheat by improving the biosynthesis and accumulation of lignin and cellulose. Under late sowing, the expression levels of key genes(Ta PAL, Ta CCR, Ta COMT, TaCAD, and TaCesA1, 3, 4, 7, and 8) and enzyme activities(TaPAL and TaCAD) related to lignin and cellulose biosynthesis peaked 4–12 days earlier, and except for the TaPAL, TaCCR, and TaCesA1 genes and TaPAL, in most cases they were significantly higher than under normal sowing. As a result, lignin and cellulose accumulated quickly during the stem elongation stage. The mean and maximum accumulation rates of lignin and cellulose increased, the maximum accumulation contents of lignin and cellulose were higher, and the cellulose accumulation duration was prolonged. Consequently, the lignin/cellulose ratio and lignin content were increased from 0 day and the cellulose content was increased from 11 days after jointing onward. Our main finding is that the improved biosynthesis and accumulation of lignin and cellulose were responsible for increasing the stem-filling degree, breaking strength, and lodging resistance. The major functional genes enhancing lodging resistance in wheat that are induced by delayed sowing need to be determined.

HbNST1 is a positive regulator of the lignin accumulation in strawflower bracts

Strawflower(Helichrysum bracteatum)capitula have papery bracts and thus have the qualities of a naturally dried flower.The involucral bract cells have a secondary cell wall(SCW)of which a crucial component is lignin.Although the constituents of SCWs have been studied extensively in plants,little is known of the mechanism regulating SCW formation,especially lignin biosynthesis in the involucral bracts of strawflower.In this study,a homolog of NAC SECONDARY WALL THICKENING PROMOTING FACTOR 1,designated Hb NST1,was identified as a positive regulator of lignin biosynthesis in strawflower.The transcript level of Hb NST1 was the highest in the involucral bracts.Subcellular localization analysis indicated that Hb NST1 was localized to the nucleus.Overexpression of Hb NST1 in Chrysanthemum indicum promoted the expression of a gene related to lignin biosynthesis,a homolog of cinnamyl alcohol dehydrogenase,designated Ci CAD,suggesting that Hb NST1 was associated with the accumulation of lignin in the SCW of the involucral bracts.Taken together,the results suggested that Hb NST1 positively regulated lignin accumulation in the involucral bracts and mediated the expression of lignin biosynthesis-related genes in strawflower.

Performance characterization, of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

The two kinds of rigid polyurethane （PU） foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight. The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams. The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples. The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently. Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples. The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

Dynamic Changes in Distribution of Lignin and Hemicelluloses in Cell Walls During Differentiation of Secondary Xylem in Eucommia ulmoides

The dynamic changes in the distribution of lignin and hemicelluloses (xylans and xyloglucans) in cell walls during the differentiation of secondary xylem in Eucommia ulmoides Oliv. were studied by means of ultraviolet light microscopy and transmission electron microscopy combined with immunogold labelling. In the cambial zone and cell expansion zone, xyloglucans were localized both in the tangential and radial walls, but no xylans or lignin were found in these regions. With the formation of secondary wall S-1 layer, lignin occurred in the cell corners and middle lamella, while xylans appeared in S-1 layer, and xyloglucans were localized in the primary walls and middle lamella. In pace with the formation of secondary wall S-2 and S-3 layer, lignification extended to S-1, S-2 and S-3 layer in sequence, showing a patchy style of lignin deposition. Concurrently, xylans distributed in the whole secondary walls and xyloglucans, on the other hand, still localized in the primary walls and middle lamella. The results indicated that along with the formation and lignification of the secondary wall, great changes had taken place in the cell walls. Different parts of cell walls, such as cell corners, middle lamella, primary walls and various layers of secondary walls, had different kinds of hemicelluloses, which formed various cell wall architecture combined with lignin and other cell wall components.

Adsorption/desorption behavior between a novel amphoteric granular lignin adsorbent and reactive red K-3B in aqueous solutions

A novel amphoteric granular lignin adsorbent(AGLA) was prepared using magnesium lignosulfonate as a raw material which was provided by a straw sulfite pulp mill in Guangdong Province, China. A reactive dye(red K-3B) was used as an adsorbate to investigate the adsorption behavior by static and mobile ways. The removal of reactive red K-3B was found to be initially pH and concentration dependent. Moreover, an increase of solution temperature ranging from 5℃ to 60℃ helped to enhance the rate of intraparticle diffusion of adsorbate and changes in the size of the pores of the adsorbent and thus to reduce the adsorption time. The total breakthrough adsorption capacity was 531 mg/g, and the saturated adsorption capacity was 560 mg/g, which prevailed over the activated carbons evidently. The reactive red K-3B adsorbed on AGLA could be recovered with a mixture of alcohol, NaCl and HCl aqueous solutions. The recovery percentage could reach 92.4%.

Oxidative Degradation of Soda Lignin Assisted by Microwave Irradiation

The effects of oxidant dosage,oxidation temperature and time on the degradation of soda lignin by hydrogen peroxide with and without the presence of microwave irradiation were investigated.It is found that the oxidative degradation of lignin includes the cleavage of ether bond inβ-O-4 structure,the partial destruction of aromatic ring,and the re-condensation of the degraded lignin.Compared to the conventionally heated oxidation of lignin,the microwave irradiation efficiently facilitates the degradation of the lignin with high molecular weight and the re-condensation of that with low molecular weight at a low oxidant dosage,low oxidation temperature,or a short oxidation time,which leads to the formation of the degraded lignin with narrower molecular weight distribution and lower molecular weight.Additionally,the lignin degraded in the presence of microwave irradiation has the characteristics of higher content of phenolic hydroxyl group,lower content of methoxyl group,and lower degree of condensation,which enhances the reactivity of lignin.Therefore,the oxidative degradation of lignin assisted by microwave irradiation may be a new pretreatment approach for efficiently utilizing the soda lignin.

Preparation of nitrogen and sulfur co-doped ultrathin graphitic carbon via annealing bagasse lignin as potential electrocatalyst towards oxygen reduction reaction in alkaline and acid media

Renewable lignin used for synthesizing materials has been proven to be highly potential in specific electrochemistry.Here,we report a simple method to synthesize nitrogen and sulfur co-doped carbon nanosheets by using bagasse lignin,denoted as lignin-derived carbon(LC).By adjusting the ratio of nitrogen source and annealing temperature,we obtained the ultrathin graphitic lignin carbon(LC-4-1000)with abundant wrinkles with high surface area of 1208 m2g_1 and large pore volume of 1.40 cm3g_1.In alkaline medium,LC-4-1000 has more positive half-wave potential and nearly current density compared to commercial Pt/C for oxygen reduction reaction(ORR).More importantly,LC-4-1000 also exhibits comparable activity and superior stability for ORR in acid medium due to its high graphitic N ratio and a direct four electron pathway for ORR.This study develops a cost-effective and highly efficient method to prepare biocarbon catalyst for ORR in fuel cells.

Catalytic transfer hydrogenolysis as an efficient route in cleavage of lignin and model compounds

Cleavage of aromatic ether bonds through hydrogenolysis is one of the most promising routes for depolymerisation and transformation of lignin into value-added chemicals. Instead of using pressurized hydrogen gas as hydrogen source, some reductive organic molecules, such as methanol, ethanol, isopropanol as well as formates and formic acid, can serve as hydrogen donor is the process called catalytic transfer hydrogenolysis. This is an emerging and promising research field but there are very few reports. In this paper, a comprehensive review of the works is presented on catalytic transfer hydrogenolysis of lignin and lignin model compounds aiming to breakdown the aromatic ethers including a-O-4, b-O-4 and 4-O-5 linkages, with focus on reaction mechanisms. The works are organised regarding to different hydrogen donors used, to gain an in-depth understanding of the special role of various hydrogen donors in this process. Perspectives on current challenges and opportunities of future research to develop catalytic transfer hydrogenolysis as a competitive and unique strategy for lignin valorisation are also provided.

Synthetic Process of Bio-Based Phenol Formaldehyde Adhesive Derived from Demethylated Wheat Straw Alkali Lignin and Its Curing Behavior

Lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendlybio-based polyphenol material. In the present work, the demethylated wheat straw alkali lignin (D-Lig), preparedby demethylation of wheat straw alkali lignin (Lig) using an in-situ generated Lewis acid, was used to synthesizebio-based phenol formaldehyde resin adhesive (D-LPF) applied in plywood. Effects of synthetic process’s factors,including lignin substitution for phenol, NaOH concentration and molar ratio of formaldehyde to phenol, on thebonding strength and free formaldehyde content of D-LPF were investigated in detail, and the optimum syntheticprocess of D-LPF was obtained as following: Lignin substitution for phenol 60%, NaOH concentration 5.0% andmolar ratio of formaldehyde to phenol 2.0, and under the optimum reaction condition, the D-LPF presented lower free formaldehyde content (0.18%) and higher bonding strength (2.19 MPa), which was better than those ofcontaining-lignin phenol formaldehyde resin adhesive (LPF). Additionally, the curing behavior of the adhesivewas studied by differential scanning calorimetry (DSC) combined with gel time. It can be obtained that D-LPFresin adhesive had the shortest gel time, and fastest curing rate, compared with those of PF and L-PF resin adhesives. The curing kinetics data was fitted well by Kissinger model using non-isothermal DSC method, and theaverage activation energy value was 85.3 kJ/mol, slightly higher than that of commercial PF resin, while lowerthan that of LPF (90.2 kJ/mol). Finally, based on the analytical results of high temperature fourier transform infrared spectroscopy (FTIR), a possible curing mechanism of D-LPF was proposed.

Evaluation and Analysis of the Effect of Lignin Amelioration on Loess Collapsibility

The road subgrade and road surface in collapsible loess area are prone to many engineering diseases such as uneven subgrade settlement,insufficient bearing capacity of soaked foundation,collapse and instability of sub-grade side slope due to the special properties of loess.As an environment-friendly,low-cost soil modifier with good adhesion and chelation properties,lignin has been considered to be used in highway subgrade construction.In order to explore the effect of lignin on loess,the compressive and collapsible properties of modified loess with different lignin contents were analyzed based on consolidation compression test.The improvement mechanism of lignin on loess collapsibility was studied by means of infiltration test and SEM test.The results show that lignin fibers can promote the agglomeration of loose particles and form a network structure in the soil particle pores,enhance the cementation strength between particles and soil skeleton,and reduce the permeability of loess.With the increase of lignin fiber content,the improvement degree of loess collaps ility shows a trend of first increasing and then decreasing.When the lignin fiber content is 2%,the effect is the best,and the improved loess ollapsi-bility is eliminated.

Predicting Levels of Crude Protein, Digestibility, Lignin and Cellulose in Temperate Pastures Using Hyperspectral Image Data

Hyperspectral sensors provide the potential for direct estimation of pasture feed quality attributes. However, remote sensing retrieval of digestibility and fibre (lignin and cellulose) content of vegetation has proven to be challenging since tissue optical properties may not be propagated to the canopy level in mixed cover types. In this study, partial least squares regression on spectra from HyMap and Hyperion imagery were used to construct predictive models for estimation of crude protein, digestibility, lignin and cellulose concentration in temperate pastures. HyMap and Hyperion imagery and field spectra were collected over four pasture sites in southern Victoria, Australia. Co-incident field samples were analyzed with wet chemistry methods for crude protein, lignin and cellulose concentration, and digestibility was calculated from fiber determinations. Spectral data were subset based on sites and time of year of collection. Reflectance spectra were extracted from the hyperspectral imagery and collated for analysis. Six different transformations including derivatives and continuum removal were applied to the spectra to enhance absorption features sensitive to the quality attributes. The transformed reflectance spectra were then subjected to partial least squares regression, with full cross-validation “leave-one-out” technique, against the quality attributes to assess effects of the spectral transformations and post-atmospheric smoothing techniques to construct predictive models. Model performance between spectrometers, subsets and attributes were assessed using a coefficient of variation (CV), —the interquantile (IQ) range of the attribute values divided by the root mean square error of prediction (RMSEP) from the models. The predictive models with the highest CVs were obtained for digestibility for all spectra types, with HyMap the highest. However, models with slightly lower CVs were obtained for crude protein, lignin and cellulose. The spectral regions for diagnostic wavelengths fell within the chlorophyll well, red edge, and 2000-2300 nm ligno-cellulose-protein regions, with some wavelengths selected between the 1600 and 1800 nm region sensitive to nitrogen, protein, lignin and cellulose. The digestibility models with the highest CV’s had confidence intervals corresponding to ±5% digestibility, which constitutes approximately 30% of the measured range. The cellulose and lignin models with the highest CV’s also had similar confidence intervals but the slopes of the prediction lines were substantially less than 1:1 indicating reduced sensitivity. The predictive relationships established here could be applied to categorizing pasture quality into range classes and to determine whether pastures are above or below for example threshold values for livestock productivity benchmarks.

Interception, degradation and contributions of terrestrial organic carbon obtained from lignin analysis in Wujiang River, southwest China

Understanding the fate of terrestrial organic carbon(OC)in a cascade impoundment system is critical for recognizing the role of carbon sink for reservoirs.Surface sediments collected from eight cascade reservoirs across the Wujiang River,southwestern China,were analyzed for elemental and stable carbon isotopic(δ^13C)composition,and lignin phenols(∑8 andΛ8)to investigate the spatial distribution,contribution,origin and degradation of sedimentary terrestrial OC.The values of total organic carbon(TOC)and∑8 exhibited a remarkable reduction along the upstream-downstream transect suggesting the trapping effect of cascade-damming.A relatively broad range ofδ^13C(-26.61 to-25.54%,95%CI)and C/N(6.80-18.20)indicated mixed allochthonous/autochthonous OC sources in surface sediments.The quantitative simulation indicates that the OC of the sediments mainly was derived from terrestrial organic matter.Soilderived OC rather than C_(3)vascular plant-derived OC makes a major contribution to sedimentary terrestrial OC in reservoirs on karst terrain.As evidenced by lignin compositions andδ^13C,the predominant vascular plant origins of terrestrial OC along the Wujiang River are non-woody angiosperm C_(3)plants.The aged reservoirs showed a trend of increasing contribution of autochthonous OC,which potentially weaken the role of carbon sink for reservoirs.The relationship between runoff inputs,watershed area/water surface area ratios,and water residence time and Λ8 were explored,indicating the natural and anthropogenic influences on terrestrial OC remains very complex in a cascade-damming river.

Performance characterization of rigid polyurethane foam with refined alkali lignin and modified alkali lignin

The two kinds of rigid polyurethane(PU) foams were prepared with respectively adding the refined alkali lignin and alkali lignin modified by 3-chloro-1,2-epoxypropane to be instead of 15% of the polyether glycol in weight.The indexes of mechanical performance, apparent density, thermal stability and aging resistance were separately tested for the prepared PU foams.The results show that the mechanical property, thermal insulation and thermal stability for PU foam with modified alkali lignin are excellent among two kinds of PU foams and control samples.The additions of the refined alkali lignin and modified alkali lignin to PU foam have little effect on the natural aging or heat aging resistance except for decreasing hot alkali resistance apparently.Additionally, the thermal conductivity of modified alkali lignin PU foam is lowest among two kinds of PU foams and control samples.The alkali lignin PU foam modified by 3-chloro-1,2-epoxypropane could be applied in the heat preservation field.

Formaldehyde Free Renewable Thermosetting Foam Based on Biomass Tannin with a Lignin Additive

This study presents easily prepared free formaldehyde bio-based foam based on a prepared thermosetting resin comprising tannin–lignin–furfuryl alcohol-glyoxal(TLFG)via mechanical stirring in presence of ether as a foaming agent.The foam was developed through a co-polycondensation reaction of glyoxal and furfuryl alcohol with condensed tannin and lignin,which is a forest-derived product.Investigation using scanning electron microscopy(SEM)showed more closed-cell structure without cracks and collapse in the TLFG foam,with a higher apparent density with respect to tannin–furanic–formaldehyde(TFF)foam.Differential scanning calorimetry(DSC),dynamic thermomechanical analysis(DTMA),and thermogravimetric analysis(TGA)investigations revealed that the curing process of TLFG foam proceeds easily even at a lower temperature.Additionally,it acquired higher heat resistance than TFF foam.Moreover,TLFG has a more robust chemical network structure,which contributes efficiently to the mechanical strength and a lower pulverization degree compared with TFF-derived foam.Fourier transform infrared spectrometry(FTIR)and electrospray ionization mass spectrometry(ESI-MS)proved that the cross-inking reactions between tannin,lignin,furfuryl alcohol,and glyoxal have been proceeded efficiently.

Synthesis of Fe^(3+)-doped Aminated Lignin as A Peroxidase Mimic for Colorimetric Detection of H_(2)O_(2) and Glucose

Peroxidase plays an important role in living systems;however,its storage difficulty and easy inactivation have limited its applications in complex environments.To address these problems,herein,we proposed a method to synthesize peroxidase mimics by amination,carbonization,and Fe^(3+)-doping of industrial alkali lignin.The Fe^(3+)-doped lignin-based peroxidase mimic(Fe-LPM),with active centers of coordination between Fe^(3+)and N atoms,showed higher tolerance to pH value and temperature than natural peroxidase.Using Fe-LPM,10-100 mmol/L of H_(2)O_(2) and glucose could be colorimetrically detected with the lowest detection limits of 80μmol/L and 1.5 mmol/L and visual detection limits of 1.0 mmol/L and 10 mmol/L,respectively.The Fe-LPM maintained peroxidase-like activity after 10 cycles and could even be used for H_(2)O_(2) detection in practical samples.This work not only provides a new approach to synthesize peroxidase mimics using biomass materials but also promotes the high-value utilization of lignin.

Application of Lignin and Its Derivatives as Slow/Controlled Release Materials in Agricultural Fields

Lignin is the main by-product of pulp and papermaking and is not effectively utilized. Conversion of industrial lignins into value-added materials is beneficial for the effective utilization of resources as well as for environmental protection. Because of their adsorptivity, slow-release property,biocompatibility, and biodegradability, lignin and its derivatives find potential applications as eco-friendly slow/controlled release materials in agricultural fields. This report reviews the recent research advances in lignin-based slow/controlled release fertilizers and pesticides.

Valorization of Kraft Lignin as Thickener in Castor Oil for Lubricant Applications

It is known that large amounts of residual lignin are generated in the pulp and paper industry.A new alternative for Kraft lignin valorization,which consists of first a chemical modification using a diisocyanate and then the efficient dispersion in castor oil to achieve stable gel-like systems,is proposed in this work.Rheological properties and microstructure of these materials were determined by means of small amplitude oscillatory shear tests and viscous flow measurements and atomic force microscopy observations,respectively.Moreover,both standardized penetration tests and tribological assays,usually performed in the lubricant industry,were carried out to evaluate the performance characteristics as lubricating greases.Linear viscoelasticity functions are affected by the lignin/diisocyanate ratio and thickener concentration.The thermorheological response evidenced a softening temperature of around 105°C.The microstructure of these gel-like dispersions is composed of interconnected thin fibers,homogeneously distributed in castor oil.Moreover,the NCO-functionalized lignin gel-like dispersions studied show lower friction coefficients than traditional lubricating greases.