Molecular Mass Distribution of Lignin from the Alkaline Pulping of Hardwood,Softwood, and Wheat Straw

Abstract

The behavior of lignin during kraft (hardwood, softwood, and wheat straw) and soda-AQ (wheat straw) pulping was studied, mainly in terms of delignification degree and molecular mass distribution (MMD). In the initial delignification phase (at 140°C for 15–60 min), a prominent part of the dissolved softwood kraft lignin (18–25 g/L, MM mostly > 3,000 Da) was found in the liquid phase of chip cavities, rather than in the external bulk black liquor (5–7 g/L, MM mostly < 3,000 Da). The maximum weight average MM values ( _w) of the soluble lignin under conventional cooking conditions were detected for the kraft softwood (4,100 Da), and kraft birch (3,400 Da) when the degree of delignification was 65–75%, corresponding to a residual lignin content of 5–10%. The maximum _w of the dissolved wheat straw kraft (5,050 Da) and soda-AQ (5,900 Da) lignins was clearly higher than that of wood-based kraft lignins (2,950–4, 100 Da).     

Fabrication of cation exchange membrane from polyvinyl alcohol using lignin sulfonic acid: Applications in diffusion dialysis process for alkali recovery

We report polyvinyl alcohol (PVA)-based hybrid membranes composed of salt of lignin sulfonic acid (LSA) and tetraethyl orthosilicate. The concentration of LSA with respect to PVA varied from 10% to 40%. The hybrid membranes showed water uptake (W_U) in the range of 122–210%, ion exchange capacities in the range of 0.32–0.75 mmol g^?1, dialysis coefficient (U_OH) from 0.0068 to 0.0119 m h^?1, and selectivity (S) from 15 to 26. The hybrid membranes also showed thermal and mechanical stability.     

Production of fuel gas and char from wood, lignin and holocellulose by carbonization

Carbonization of lignin and holocellulose extracted from the parent wood was carried out in the temperature range 400–900 °C using a small scale electric furnace to compare the yields of gas, char, tar and condensed liquid. The tar yield was < 1 % at 700 °C from the holocellulose and 4% from the wood and the lignin. The composition of the gas and the calorific value of the char produced were also measured and the conversion rate from raw wood to gas or char on the energy base was estimated from these experimental results. Finally, the heat of the reaction of carbonization was estimated from these experimental results. Carbonization of waste wood, lignin and holocellulose is exothermic, 2.1–4.8, 1.9–5.9 and 3.1–5.9 MJ kg⁻¹, respectively.     

木质素制备生物液体燃料进展

木质素中含有丰富的芳环结构,可以作为可持续再生的原料用于生产高值能源及化工品。但由于木质素结构复杂,现阶段用于制备生物液体燃料仍处于探索阶段。本文首先介绍了木质素通过催化热解、催化氢解、催化氧化3种解聚方式制备生物液体燃料的进展,分析了当前解聚产物存在低碳原子数、高氧含量的不足而导致其难以投入生产使用的现状,指出应通过C—C偶联方法（包括羟醛缩合、烷基化反应、寡聚反应以及Diels-Alder 反应）增加产物碳原子数、使用加氢脱氧（hydrodeoxygenation, HDO）工艺以降低产物氧含量,从而实现由木质素制备高密度生物液体燃料。最后对当前木质素制备高密度燃料所面临的挑战以及未来研究趋势进行了总结与展望,指出构建高效催化体系,耦合解聚、C—C偶联和HDO过程,将是该领域未来研究重点。     

Effect of bed material,lignin content,and origin on the processability of biomass in fast pyrolysis reactors

Lignin has great potential for the production of valuable aromatic compounds and has attracted considerable attention. The development of high value applications for Kraft lignin would boost the profitability of pulp and paper operations. A potential solution is the pyrolytic conversion of lignin to valuable liquids and solids. However, Kraft lignin is a thermally sensitive powder which tends to agglomerate under pyrolysis conditions. A mechanically fluidized reactor (MFR) can be used to monitor both the generation of vapours and gas during pyrolysis and how cohesive a feedstock becomes when pyrolyzed. The MFR was, therefore, used to evaluate alternative solutions to improve Kraft lignin behaviour by mixing it with non‐problematic feedstocks or by modifying its bed material. Finally, Kraft lignin behaviour and products were compared to those of hydrolysis lignins from different origins.     

撞击对稀碱液去除稻草秸秆木质素过程中的强化作用

SO₃微热爆联合稀碱液处理秸秆可在较低温度和常压下达到良好的预处理效果,为了实现该技术的进一步放大,本文对撞击对碱处理去除木质素过程的影响进行了研究。以稻草秸秆为原料,对常温下碱处理去除木质素的过程进行了研究,并讨论了温度对这一过程的影响作用。通过模拟碱液和秸秆在中试反应器中的撞击运动,探讨了撞击对碱处理去除木质素过程的影响以及不同温度下撞击的影响,并通过SEM和XPS对秸秆进行分析,解释了撞击对碱处理过程的影响机制。结果表明：常温下木质素去除过程耗时长、效率低,通过升高温度可有效提高木质素去除效率,但温度的升高会导致半纤维素损失迅速增大。而撞击可通过破坏秸秆表面产生裂隙,暴露更多木质素从而强化木质素去除过程,且在较低温度下撞击的强化作用更明显。在20℃下处理1.5h并施加450次撞击相比无撞击可使木质素去除率增加24.74%。     

Physicochemical characterization of lignin recovered from microwave‐assisted delignified lignocellulosic biomass for use in biobased materials

Lignocellulosic biomass (Moso Bamboo, Chinese tallow tree wood, switchgrass, and pine wood) was subjected to a novel delignification process using microwave energy in a binary glycerol/methanol solvent. The physicochemical properties of the recovered lignin were analyzed prior to its application in the fabrication of polylactic acid (PLA)–lignin composites. The results showed that the samples had a high Klason lignin content (>75%) and retained their natural structure. Thermogravimetric analysis revealed that the recovered lignin exhibited a different thermal decomposition pattern from that of commercial lignins. All the recovered lignins had good solubility in common organic solvents (acetone, 1,4‐dioxane, THF, DMSO, and ethanol/water) and 1 mol/L NaOH solution. The addition of lignin into the PLA matrix resulted in the improvement in tensile properties of PLA–lignin composites. PLA films with low lignin content had good UV light‐resistant properties, indicating that the recovered lignin has potential in packaging of light‐sensitive products. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42635.     

Acidic pretreatment of wheat straw in decanol for the production of surfactant, lignin and glucose

Wheat straw is an abundant residue of agriculture which is increasingly being considered as feedstock for the production of fuels, energy and chemicals. The acidic decanol-based pre-treatment of wheat straw has been investigated in this work. Wheat straw hemicellulose has been efficiently converted during a single step operation into decyl pentoside surfactants and the remaining material has been preserved keeping all its promises as potential feedstock for fuels or value added platform chemicals such as hydroxymethylfurfural (HMF). The enzymatic digestibility of the cellulose contained in the straw residue has been evaluated and the lignin prepared from the material characterized. Wheat-based surfactants thus obtained have exhibited superior surface properties compared to fossil-based polyethoxylates decyl alcohol or alkyl oligoglucosides, some of which are largely used surfactants. In view of the growing importance of renewable resource-based molecules in the chemical industry, this approach may open a new avenue for the conversion of wheat straw into various chemicals.     

Homology modeling of a heme protein, lignin peroxidase, from the crystal structure of cytochrome c peroxidase

A 3-dimensional model of lignin peroxidase (LiP) was constructedbased on its sequence homology with other peroxidases, particularlycytochrome c peroxidase, the only protein with a known crystalstructure in the peroxidase family. The construction of initialconformations of insertions and deletions was assisted by secondarystructure predictions, amphipathic helix predictions, and considerationof the specific protein environment. A succession of moleculardynamics simulations of these regions with surrounding residuesas constraints were carried out to relax the bond lengths andangles. Full protein molecular dynamics simulations with explicitconsideration of bound waters were performed to relax the geometryand to identify dynamically flexible regions of the successivemodels for further refinement. Among the important functionallyrelevant structural features predicted are: (i) four disulfidebonds are predicted to be formed between Cys3 and Cys15, Cys14and Cys285, Cys34 and Cys120 and Cys249 and Cys317; (ii) a glycosyla-tionsite, Asn257, was located on the surface; (iii) Glu40 was predictedto form a salt bridge with Arg43 on the distal side of the hemeand was considered as a possible origin for the pH dependenceof compound I formation; and (iv) two candidate substrate bindingsites with a cluster of surface aromatic residues and flexiblebackbones were found in the refined model, consistent with thenature of known substrates of LiP. Based on these predictedstructural features of the model, further theoretical and experimentalstudies are proposed to continue to elucidate the structureand function of LiP.     

Elucidation of the interaction among cellulose,xylan, and lignin in steam gasification of woody biomass

The reaction mechanism for gas and tar evolution in the steam gasification of cellulose, lignin, xylan, and real biomass (pulverized eucalyptus) was investigated with a continuous cross‐flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. In the steam gasification of real biomass, the evolution rates of water‐soluble tar (derived from cellulose and hemicelluloses) and water‐insoluble tar (derived from lignin) decrease with increasing reaction time. It was found that the evolution of water‐soluble tar occurs earlier than in the gasification of pure cellulose, indicating an interaction of the three components. The predicted yield of water‐insoluble tar is substantially less than that of real biomass. This implies that the evolution of tar from the lignin component of biomass is enhanced, compared with pure lignin gasification, by other components. The gas evolution rate from real biomass is similar to that predicted by the superposition of cellulose, lignin, and xylan. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Effect of lignin removal on mechanical,thermal, and morphological properties of polylactide/starch/rice husk blend used in food packaging

The aim of this work was to investigate the possibility of using cost‐effective natural filler in a biodegradable polymer and find new set of materials for green biocomposites to be used in food packaging. In this regard, rice husk (RH) and bleached rice husk (BRH) have been used in the form of powder and the effect of lignin removal on mechanical and thermal properties of prepared composites with poly(l ‐lactide) and starch were studied. Using FTIR technique, the lignin removal from RH has been approved. The tensile, charpy impact, and hardness tests were implemented to investigate the mechanical properties. It was concluded that filler caused increase both in the toughness and the Young modulus of samples. It was also found that the lack of lignin in BRH samples improves the mechanical properties. It was clearly observed that the BRH samples show larger modulus, charpy impact strength, and hardness compared to those filled with RH. Despite larger values for the elongations at break of RH samples, the mechanical properties showed a significant improvement (between 25 and 50% improvements) on lignin removal. The differential scanning calorimetry thermograms revealed an improvement in crystallization behavior and reduction of T_g from 47 to 31°C in the case of BRH‐filled samples. Finally, due to the removal of toxic lignin in the samples and modification of mechanical properties by this method, the BRH could have the ability of wide use in the bioplastics and food packaging industries. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41095.     

Controllable ring‐opening polymerization of trimethylene carbonate catalyzed by aliphatic tertiary amines in the presence of benzyl alcohol or F127

With the increased awareness of avoiding residue metals, the field of organocatalysts is attracting more attention. Aliphatic tertiary amines, such as triethylamine (TEA), N, N, N, N‐tetramethylethylenediamine (TMEDA) and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDTA), have low boiling points which allow their easy elimination after a chemical reaction. Here, we used these aliphatic tertiary amines to catalyze ring‐opening polymerizations (ROPs) of trimethylene carbonate (TMC). In the presence of benzyl alcohol, the catalytic activities of the tertiary amines were in the order of TEA < TMEDA < PMDTA. Correlation between the molecular weight of polycarbonates and monomer conversions was linear, suggesting the polymerization was controlled. The polymerization pathway was presumed to follow an alcohol‐activated mechanism according to the end‐group fidelity determined using ¹H NMR spectroscopy. The ROP of TMC was also successfully initiated by PEO₉₉‐PPO₆₅‐PEO₉₉ (F127) under the catalysis of the tertiary amines, producing well‐defined PTMC_n‐F127‐PTMC_n copolymers with narrow dispersity ( ca 1.2) and with thermosensitive properties in aqueous solution. Furthermore, copolymerizations of TMC with acryloyl‐containing cyclic carbonate were catalyzed by the tertiary amines in the presence of F127. No crosslinking reactions were detected. Our results demonstrate that the aliphatic tertiary amines have the potential to catalyze TMC homo‐ or copolymerization featuring controllable structure and composition under mild conditions. Copyright © 2012 Society of Chemical Industry     

Lignin Synthesis,Affected by Sucrose in Lotus (Nelumbo nucifera) Seedlings,Was Involved in Regulation of Root Formation in the Arabidopsis thanliana

Adventitious roots (ARs) have an unmatched status in plant growth and metabolism due to the degeneration of primary roots in lotuses. In the present study, we sought to assess the effect of sucrose on ARs formation and observed that lignin synthesis was involved in ARs development. We found that the lignification degree of the ARs primordium was weaker in plants treated with 20 g/L sucrose than in 50 g/L sucrose treatment and control plants. The contents of lignin were lower in plants treated with 20 g/L sucrose and higher in plants treated with 50 g/L sucrose. The precursors of monomer lignin, including p-coumaric acid, caffeate, sinapinal aldehyde, and ferulic acid, were lower in the GL50 library than in the GL20 library. Further analysis revealed that the gene expression of these four metabolites had no novel difference in the GL50/GL20 libraries. However, a laccase17 gene (NnLAC17), involved in polymer lignin synthesis, had a higher expression in the GL50 library than in the GL20 library. Therefore, NnLAC17 was cloned and the overexpression of NnLAC17 was found to directly result in a decrease in the root number in transgenic Arabidopsis plants. These findings suggest that lignin synthesis is probably involved in ARs formation in lotus seedlings.     

Formation,conversion, and elimination of intermediate spinel phase in MgO/kaolin mixture firing for cordierite

Cordierite ceramic is usually used for diesel particulate filter owing to its excellent low thermal expansion coefficient and high thermal shock resistance properties. However, the co-exited intermediate spinel phase can deteriorate the thermal and mechanical performances of cordierite ceramic product, because the spinel phase has much higher thermal expansion coefficient comparing to that of cordierite. In this study, two methods are utilized to reduce the spinel impurity in the cordierite ceramic. On the one hand, rational reaction resources were introduced to decrease spinel production. The formation of intermediate spinel phase is systematically researched by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman characterizations and the results clarified the preference of path “Enstatite + Mullite → Cordierite” for less spinel production in comparison to path “Enstatite + Al₂O₃ → Cordierite + Spinel.” Additionally, MgO was introduced as fluxing agent to promote liquid-phase sintering, thus facilitating the conversion of spinel. On the other hand, the sintering schedule was improved by introducing a holding temperature gradient to promote the diffusion of Si⁴⁺ and further promote the conversion of spinel into cordierite. With these methods, the residual spinel phase is minimized, the resulting high-purity cordierite has a 47% reduction in the thermal expansion coefficient from 3.07 × 10⁻⁶/K to 1.63 × 10⁻⁶/K compared to the original cordierite sample.     

Solution‐state NMR analysis of hydroxymethylated resorcinol cured in the presence of crude milled‐wood lignin from Acer saccharum

Resorcinol‐formaldehyde adhesives can reinforce stress fractures that appear from wood surface preparation. Researchers have found that applying the resorcinol‐formaldehyde prepolymer, hydroxymethylated resorcinol, to the surface of wood improves the bond strength of epoxy and polyurethane adhesives to wood. Hydroxymethylated resorcinol is thought to plasticize lignin components and stabilize stress fractures through reactions with lignin subunits and hemicelluloses in wood. In this study, a dilute solution of hydroxymethylated resorcinol (HMR) is cured in the presence of a crude milled‐wood lignin (cMWL) from Acer saccharum and subsequently dissolved in dimethylsulfoxide‐d₆ to delineate reactivity with lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan using solution‐state NMR spectroscopy. ¹H–¹³C single‐bond correlation NMR experiments revealed that the HMR only formed 4,4′‐diarylmethane structures with itself in the presence of the cMWL; the 2‐methylols that formed remained free and did not crosslink with resorcinol. Cured HMR resin formed both 4,4′‐ and 2,4‐diarylmethane structures, confirming that the presence of lignin and O‐acetyl‐(4‐O‐methylglucurono)xylan hinders crosslinking at the C‐2 position. No evidence of reactivity between HMR and lignin subunits was found. New peaks consistent with ester linkages were observed in ¹³C‐NMR spectra of the cMWL sample treated with HMR that may be attributable to HMR moieties condensing with glucuronic acid substituents. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45398.     

Enzymatic acidolysis in hexane to produce n−3 or n−6 FA-enriched structured lipids from coconut oil: Optimization of reactions by response surface methodology

Response surface methodology is a statistical design that helps one to determine optimal conditions for an enzyme-catalyzed reaction by performing a minimal number of experiments. This methodology was adapted for modifying coconut oil TAG by using lipase-catalyzed acidolysis in hexane to incorporate n−3 or n−6 PUFA. FFA obtained after hydrolysis of cod liver oil and safflower oil were used as acyl donors. Immobilized lipase, Lipozyme IM60, from Rhizomucor miehei was used for catalyzing the reaction. The reaction conditions—substrate molar ratio, incubation time, and temperature—were optimized. The experimental data were fitted to a response function based on the central composite rotatable design. The optimal conditions generated from models indicated that maximal incorporation of n−3 PUFA occurred at a 1∶4 molar ratio of TAG/FFA when incubation was carried out for 34 h at 54°C. Similarly, maximal incorporation of n−6 FA was predicted at a 1∶3 molar ratio of TAG/FFA when incubated for 48.5 h at 39°C. Experiments conducted at optimized conditions predicted by the equation obtained from response surface methodology yielded structured lipids with 13.65 and 45.5% of n−3 and n−6 FA, respectively. These values agreed well with that predicted by the model. The reactions were also scaled up to 100 g levels in batch reactors with the incorporation level of n−3 and n−6 fatty acids agreeing closely with that observed when the reactions were carried out at lab scale (100 mg). These studies indicated that response surface methodology is a useful tool in predicting the conditions for incorporating desired levels of specific FA during the synthesis of structured lipids.     

The Effect of 7 H -Dibenzo[ c,g ]carbazole and Benzo[ a ]pyrene Mixture on DNA Adduct Formation in Strain A/J Mouse Model: Preliminary Report

Complex mixtures consist of homocyclic and heterocyclic polycyclic aromatic compounds (PACs) represented by benzo[ a ]pyrene (B a P) and 7 H -dibenzo[ c,g ]carbazole (DBC), respectively. To exert their biological effects, PACs are metabolized into reactive intermediates, which can form DNA adducts. In this preliminary report, male A/J mice were given a single intraperitoneal injection. Groups of three animals were treated with DBC (2 or 10 mg/kg) or B a P (10 or 100 mg/kg). Mixtures of DBC:B a P were given at doses of 2:10, 2:100, 10:10, or 10:100 mg/kg. DNA adduct levels in lungs collected three days posttreatment were determined by the 32 P-postlabeling method. The results indicate that, in the lungs, exposure to mixtures containing more B a P than DBC resulted in the absence of adduct 3 (DBC) and significantly higher total adduct levels. This suggests that B a P is being preferentially metabolized, resulting in less DBC adduction.     

Is it possible to predict gas yields of any biomass after rapid pyrolysis at high temperature from its composition in cellulose, hemicellulose and lignin?

Ligno-cellulosic biomass from different sources presents very variable compositions. Consequently, there is a wide variation in the nature and quantities of gaseous products obtained after thermal treatment of biomasses.The objective of this work is to establish a link between the composition of a biomass and its pyrolysis gas yields and composition. Experimental flash pyrolysis of several biomasses at a temperature of 950 °C and a gas residence time of about 2 s was carried out. An attempt was then made to predict gas yields of any biomass according to its composition. We show that an additivity law does not allow the gas yields of a biomass to be correlated with its fractions of cellulose, hemicellulose and lignin. Several potential explanations are then offered and quantitatively demonstrated: it is shown that interactions occur between compounds and that mineral matter influences the pyrolysis process.     

Effect of steam-drying treatment on moisture content,drying rate,color, and drying defects in juvenile wood of Tectona grandis from fast-growth plantations

Tectona grandis is the second most important species for reforestation in Costa Rica, and any improvement in its industrialization process is important, especially the drying process. Lumber obtained from a plantation of 12-year-old T. grandis trees was used to evaluate three drying schedules that include integrated steaming processes to determine the combined effect of the steam-drying system on the dried lumber. The variations in the moisture content (MC) and drying rate (DR) with drying time (DT) both before and after the steaming process were modeled mathematically for boards that have a flat and quarter grain pattern. For both types of boards that were dried with and without steaming, a relationship between MC and DT was observed. There was inflexion at 40%, and two mathematical models were computed. Additionally, the relationship between DR and DT for boards with flat and quarter grain patterns was not affected by the steaming process, and an inflection point was observed at 30?h (40% MC for the lumber). Moderate changes were observed in the CIELAB color system and dried lumber became darker. The steaming process, which was integrated in the drying schedule for boards with the flat and quarter grain pattern, decreased the incidence or magnitude of drying defects depending on the grain pattern and drying schedule used.