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Amino alkylation of technical lignins via the Mannich reaction can be used as an analytical derivatization technique, but it is also used to improve kraft lignin hydrophilicity or metal ion adsorptive capacity. Recent studies have indicated the potential for increased amination under acidic conditions; however, the effects of pH on the amination of kraft lignins remain poorly understood because indirect quantification methods are often used. A quantitative technique combining 2D HSQC NMR and 13C NMR spectroscopy was used in this study to directly probe the structure of high and low molecular weight fractions of an industrial pine kraft lignin aminated in acidic or basic media with dimethylamine or diethylamine. The degree of amine substitution was two times higher for low molecular weight lignin compared to the high molecular weight fraction. Neither pH nor amine species had any significant effect. New evidence confirms that amine substitution of pine kraft lignin takes place selectively ortho to non-etherified phenolic hydroxyl groups and displaces carboxylic acid groups of benzoic- and cinnamic-type subunits. Other pathways were proposed and tested, but substitution did not occur at sterically hindered sites. Elemental analysis has been the most widely used indicator of Mannich condensation, but unfortunately overestimates amine substitution because nitrogen-containing side products and impurities can be included in the total nitrogen content. Multiple methods should always be employed when characterizing complex, heterogeneous biopolymers like lignins to avoid misinterpretation of results.

Plasticizers depress the glass transition temperature (Tg) of polymers and produce a flowable material at lower temperatures. The use of plasticizers to depress Tg of lignin is important, since at high processing temperatures lignin crosslinks, making it intractable. The goal of this study was to assess plasticizers and polymer blends for the ability to retard a commercial softwood kraft lignin from crosslinking and also serve as thermal and rheological property modifiers during thermal processing in the attempt to produced moldable and spinnable lignin for lignin and carbon fiber products. The Tg of the lignin and the lignin mixed with various amounts of plasticizers and with different thermo-mechanical mixing were determined using differential scanning calorimetry. The Tg and the change in heat capacity at the glass transition (ΔCp) decreased and increased, respectively, about linearly within this plasticizers range with increased plasticizer weight percentage. Gel permeation chromatography results for extruded lignin as well as extruded lignin-plasticizer blends with glycerol, N-allyurea, citric acid with and without sodium hypophosphite, and oleic acid indicate that the presence of these materials reduced the rate of molecular weight increase at temperatures between 100 and 200 °C. Continuous, homogenous films and fibers could be produced by thermal processing with plasticized lignin samples and plasticized lignin-polymer blends, but not with lignin alone. These fibers could be carbonized, yielding up to about 50% of carbon. The present findings have shown the advantages of plasticizers in thermally processing a commercial softwood kraft lignin.

Lignin is a by-product of the pulp and paper industry that can be precipitated by acidification from black liquor as a potential feedstock for valuable green materials. Precipitation and quantification of lignin from softwood black liquors have been documented and commercialized with well-established methods; however, applying those methods to the precipitation of lignin from hardwood black liquors has produced low lignin yields. A need to understand the main differences between hardwood and softwood lignin precipitation prompted the current investigation. Multiple black liquor samples from sweetgum and pine pulping were obtained at different times of standard kraft cooks. Two lignin fractions were precipitated from each of these black liquors, one at pH 9.5 and one at pH 2.5. Detailed lignin and carbohydrate material balances were performed around each of the sample sets, starting with the wood and ending with precipitated lignin fractions. For all conditions tested, the amount and purity of pine lignin precipitated were superior to sweetgum lignin. The maximum recovery for sweetgum lignin was 69.7%, while for pine lignin, it was 90.9%.

Softwood pulp is more recalcitrant toward enzymatic hydrolysis than hardwood or nonwood pulps. Pulps of various kappa numbers were prepared from loblolly pine chips by kraft cooking, which was foll...

Lignin, an abundant renewable aromatic biopolymer, is an essential macromolecule in terrestrial vascular plants. Genetic modifications affecting monolignol biosynthesis, which produces lignin monom...

Fractionation represents a promising methodology to refine technical lignin and facilitate lignin valorization. Many lignin fractionation processes have been developed on a laboratory scale, but none have been implemented on a commercial scale. The current publicly available technical and financial performance analyses regarding industrial-scale lignin fractionation are insufficient to justify its feasibility. Herein, we report our detailed techno-economic analysis to provide knowledge and insights into industrial-scale lignin fractionation. Laboratory-scale experiments were performed to collect inputs for process simulation. The solvents were selected based on lignin solubility, potential for commercialization and environmental impacts. Fractionated lignins were thoroughly characterized and their properties exhibited good correlation with molecular weight. The economic analysis revealed that the capital expenditures for a co-located lignin fractionation facility ranged from 20 to 32 million USD, with an operational expenditure between 390 and 460 USD per t. The major operational cost drivers were determined to be raw lignin, solvent make-up, and depreciation. The minimum product selling prices for the low molecular weight fraction were estimated to be between 700 and 1000 USD per t, assuming the high molecular weight fraction has the same value as raw lignin. Sensitivity analysis indicated that the facility scale, the solvent losses, and the raw lignin cost have major impacts on capital expenditures and operational expenditures.

Efficient cleavage of aryl–ether linkages is a key strategy for generating aromatic chemicals and fuels from lignin. Currently, a popular method to depolymerize native/technical lignin employs a combination of Lewis acid and hydrogenation metal. However, a clear mechanistic understanding of the process is lacking. Thus, a more thorough understanding of the mechanism of lignin depolymerization in this system is essential. Herein, we propose a detailed mechanistic study conducted with lignin model compounds (LMC) via a synergistic Co–Zn/Off-Al H-beta catalyst that mirrors the hydrogenolysis process of lignin. The results suggest that the main reaction paths for the phenolic dimers exhibiting α-O-4 and β-O-4 ether linkages are the cleavage of aryl–ether linkages. Particularly, the conversion was readily completed using a Co–Zn/Off-Al H-beta catalyst, but 40% of α-O-4 was converted and β-O-4 did not react in the absence of a catalyst under the same conditions. In addition, it was found that the presence of hydroxyl groups on the side chain, commonly found in native lignin, greatly promotes the cleavage of aryl–ether linkages activated by Zn Lewis acid, which was attributed to the adsorption between Zn and the hydroxyl group. Followed by the cobalt catalyzed hydrogenation reaction, the phenolic dimers are degraded into monomers that maintain aromaticity.

Biphenyl linkage is the second most abundant linkage in softwood lignin; the β-O-4′ linkage being the most abundant linkage. That about 20–28% of monolignols are linked by biphenyl linkage has been...

Chips from E. urophylla x E. grandis hybrid were subjected to kraft cooking using two different approaches: low and high residual effective alkali. The lignin remaining in the pulps were analyzed f...

The extractability of hemicellulose from different lignocellulosics depends on the source of biomass. Differences in hemicellulose extractability are believed to be due to plant-specific hemicellulose arrangement alongside lignin within the cell wall. In this research, six biomasses were used to probe hemicellulose alkaline extractability as a function of the native lignin within the biomasses. Quantitative 2D-HSQC and 13C NMR analysis were performed to determine the S/G (S: syringyl, G: guaiacyl) and lignin-carbohydrate complex (LCC) linkages of milled wood lignin isolated from these biomasses. A strong negative correlation was observed between total lignin content and hemicellulose extractability, demonstrating that a greater presence of lignin in the original material results in lower xylan solubilization. In addition, a correlation between S/G of lignin and xylan dissolution was found within a group of hardwoods and within a group of non-woods. This suggests that monomeric constituency also influences xylan’s propensity for dissolution in 10% NaOH. Although there is some uncertainty in the quantification of LCC linkages, both non-woods and hardwoods exhibited negative correlations between alkaline-stable LCC linkages content and xylan extractability. This suggests that alkaline-stable LCC structures are associated with a decrease in the alkaline extractability of hemicellulose.

Phenolation can effectively improve the reactivity of lignin by directly increasing the phenolic hydroxyl groups and reactive sites for adhesive applications. Wheat straw residue isolated from an autohydrolysis/refining/enzymatic hydrolysis process was phenolated to improve the reactivity of lignin. The optimum phenolation conditions were determined to be a lignin/phenol (L/P) ratio of 1/3 with a 10% acid charge at 120 °C for 2 hours. Phenolated lignin resulted in 32 wt% of phenol incorporated onto lignin and a significant decrease in molecular weight. A comprehensive characterization indicated that all lignin substructures (β-O-4′, β-5′/α-O-4′, β-β′, ferulate, p-coumarate and p-benzoate) were reacted along with a hydrolysis of over 50% of polysaccharides during phenolation, resulting in a decrease in aliphatic hydroxyl groups and an increase in the phenolic hydroxyl groups. Phenol was incorporated onto both the sidechains and aromatic nuclei. These improvements in lignin reactivity will enable it to be used in adhesives with higher substitution rates.

Changes to the molecular properties of lignin over the course of biorefinery processing were investigated by using sweetgum as a feedstock. Hydrothermal pretreatment has been used because it is an economically attractive, green process. Three representative biorefinery lignin preparations were obtained, with about 70 % yield based on raw lignin. The three fractions included soluble lignin adsorbed on resin (XADL), solvent-extracted lignin (HTCELp), and an additional ball-milled residual lignin (HTRELp). By comparing the raw and biorefinery lignin preparations, it can be concluded that lignin undergoes both degradation and condensation throughout the various stages of the hydrothermal-based biorefinery process. The two fractions made soluble by biorefinery processing, XADL and HTCELp, were found to be low-molecular-weight degradation products enriched with free phenolic hydroxyl groups. In addition, about 15 % of noncondensed phenolic units were involved in condensation reactions. Quantitative NMR spectroscopy analysis revealed that at least about 28 % of β-O-4' substructures were cleaved. Hibbert's ketones were identified in XADL and HTRELp, which provided evidence of lignin undergoing acidolysis. The contents of β-5' and β-β' did not change significantly upon biorefinery processing. Finally, episyringaresinol was detected in XADL and HTCELp. It is hoped that these findings will help to further demonstrate the specific effects of biorefinery processing on lignin in hardwood and facilitate its utilization to improve biorefinery economics.

In this study, a novel modified nickel/H-beta (Ni/DeAl-beta) catalyst, which has active acidic sites and hydrogen binding sites, was prepared and used to produce liquefied fuel from lignin. The bifunctional Ni/DeAl-beta catalyst efficiently converted kraft lignin into liquefied fuel due to the synergistic effect of aluminum Lewis acid sites and nickel hydrogen binding sites. At a nickel content of 0.6 mmol/gzeolite, the Ni/DeAl-beta catalyst gave a high liquid product yield of 88.6% at 300 °C for 36 h. Most of the liquid product was dissolved in petroleum ether (73% of 88.6%), which was mainly composed of monomeric and dimeric degradation products. Under these conditions, the higher heating values (HHV) increased from 24.9 MJ/kg for kraft lignin to 32.0 MJ/kg for the liquid product. These results demonstrated the bifunctional Ni/DeAl-beta catalyst could be an efficient catalyst for lignin to liquefied fuel conversion.

Lignin is a complex natural polymer and by-product of the pulp and paper industry. Currently, the increasing interest in bio-based products has motivated the search for alternative renewable feedstocks that can sustainably replace synthetic polymers. Because of the phenolic functionalities of lignin, this natural polymer has attracted interest for application in biomaterials. Among various products, polymeric foams stand out as a potential product in which lignin incorporation has resulted in improved mechanical and thermal properties. This paper reviews the state of lignin foam development, with emphasis placed on phenol-lignin types.

The present work focused on characterizing the chemical and structural properties of isolated lignin from six hardwoods and their kraft pulps in an attempt to better understand the relationship between lignin’s chemical properties and resultant oxygen delignification performance. Several hardwood samples were cooked under the same conditions with varying alkali charges to obtain unbleached pulps with kappa numbers between 19 and 20. These pulps were then subjected to an oxygen delignification stage. Both processes were evaluated for pulp quality, residual lignin, and O-stage delignification efficiency. The oxygen delignification stage was carried out under fixed conditions and evaluated with regards to kappa number, which was corrected for hexenuronic acid (HexA) contributions.Results revealed that different hardwood species exhibited differing oxygen delignification efficiencies. A high correlation was found between the O-stage delignification efficiency and the content of phenolic groups in the unbleached lignin, which confirmed that free phenolic groups are the reactive site for molecular oxygen attack. When different hardwood species were compared, the HexA contents were not found to affect O-stage delignification efficiencies.

Hemicellulose is an abundant and underutilized carbohydrate polymer in plants. The objective of this study was to understand the effect of delignification on hemicellulose extraction efficiency with different types of lignocellulosic biomass. In the case of pine, with a prior sodium chlorite or peracetic acid delignification, more than 50% of the original hemicellulose in the biomass could be extracted using a 10% sodium hydroxide solution; without delignification, only 3.4% of hemicellulose could be extracted from pine. In contrast, without prior delignification, acceptable hemicellulose extraction efficiencies (55.5% and 50.7%, respectively) were achieved from switchgrass and poplar. In addition, the effect of hemicellulose extraction processes on the enzymatic convertibility of the cellulose-rich residues after extraction was determined. The cellulose-rich residues from switchgrass after hemicellulose alkali extraction showed high glucose recovery with enzyme hydrolysis with or without prior delignification. For pine and poplar, high glucose recovery with enzyme hydrolysis of the cellulose-rich residues only occurred if the sample had a delignification step prior to hemicellulose extraction. This information on commercially available biomass feedstocks is useful for those considering isolating hemicellulose within a biorefinery concept.

Phenolation can be used to improve the reactivity and decrease the molecular weight of lignin, thereby making it more useful for various applications. We report an effective phenolation process with only a catalytic amount of sulfuric acid and using phenol as solvent. The optimum phenolation conditions for pine kraft lignin and sweetgum biorefinery lignin were determined to be lignin/phenol (L/P, wt/wt) of 3/5, 5% acid charge at 90 °C for 2 h and L/P of 2/5, 5% acid charge at 110 °C for 2 h, respectively. Phenolation resulted in introducing 30 wt % of phenol onto pine kraft lignin and 60 wt % of phenol onto sweetgum biorefinery lignin and significantly decreasing in the molecular weight of lignin. Phenol was incorporated onto both the side chains and aromatic nuclei of lignin. All lignin substructures of β-O-4′, β-5′/α-O-4′, β–β′, α-carbonyl, etc. were reacted, resulting in a significant decrease in aliphatic hydroxyl groups and increase in the phenolic hydroxyl groups. The comprehensive characterization ...

Biomass hydrolysate, rich in glucose, was used to produce an important platform chemical, 5-hydroxymethylfurfural (HMF). By separating the solid biomass from solution after autohydrolysis, most of the inhibitors were removed from hydrolysate. Biphasic system, which prevents the HMF degradation, was optimized with HCl and AlCl3 catalysts. The yield of HMF conversion using biomass hydrolyzate under the optimized reaction conditions is comparable to the yield using pure glucose as a feedstock. This lab-generated HMF was purified via activated charcoal and oxidized to high value-added chemical, 2,5-furandicarboxylic acid (FDCA). The final FDCA yield of 65% was achieved. The results suggest that, with the separation of nonsugar components such as dissolved lignin and sugar degradation products, biomass hydrolysate is a promising source for HMF and FDCA production.

The lignin rendered soluble by lignocellulosic biorefinery pretreatment remains insufficiently understood along the lines of molecular properties and chemical composition. To procure a representative soluble lignin preparation, an aromatic-selective adsorptive resin was utilized. Approximately 90% of soluble lignin could be recovered from autohydrolysis pretreatment hydrolyzate (autohydrolyzate) produced from a hardwood and a nonwood biomass. Adsorbate compositional characterization revealed a befuddling magnitude of carbohydrate in selectively isolated lignin adsorbates. Quantitative structural analysis of the lignin by NMR suggested lignin–carbohydrate complexes (LCCs) as the cause behind the pronounced carbohydrate contents. Analyzed spectra revealed both hardwood and nonwood soluble lignin features of ∼10 total LCC per 100 aromatic rings, with each lignin bearing unique LCC profiles. In addition, native structures remained in large quantities. The improved understanding of hydrolyzate-soluble lignin g...

An international seminar on lignin biodegradation was held May 9 to 11, 1978, at the US Forest Products Laboratory in Madison, Wisconsin. This book records the proceedings of that seminar and is meant to provide a state-of-the-art summary of research. Each speaker/author was asked to summarize his research, including his latest unpublished results, and to describe how his work fits into the overall picture. Following two orientation chapters, one a review of lignin structure and morphological distribution in plant cell walls, and the second a review of the microbial catabolism of relevant aromatics, the book is comprised of chapters in the three subject areas given by the book's title. It does, as intended, provide comprehensive coverage of research to date. Separate abstracts have been prepared of each item for inclusion in the Energy Data Base.

Hybrid poplars (Populus nigra L. × Populus maximowiczii A.) were genetically modified through antisense insertion of the 4-coumarate:coenzyme A ligase (4CL) gene. Compositional changes in response to this genetic change were measured in the field after 2 and 3 years of growth. The stem samples were treated with either green liquor or dilute acid pretreatments, representing alkaline and acid pretreatments. The enzymatic saccharification of the untreated and pretreated transgenic poplars were evaluated. After transgenic species were transplanted into the environment, they showed reduced recalcitrance to chemicals (i.e., pretreatments) and enzymes despite their lignin content and S/V ratio being comparable to those of the wild types. Compared to the field-grown poplars, the sugar yield increased up to 103% for untreated transgenic samples and increased 22% for acid- and green liquor-pretreated transgenic samples. This shows that field-grown transgenic hybrid poplars with modified lignin biosynthesis have imp...

Biomass derived 5-hydroxymethylfurfural (HMF) is regarded as an important platform molecule for the synthesis of value-added chemicals and fuels, but the high production cost has always been a bottleneck for the industrial scale use of HMF. Different mineral acids (HCl and H2SO4) being used as the catalyst and different salts being used as the reaction promoter were evaluated. It was found that HCl, in combination with NaCl, in a water/γ-valerolactone system showed high selectivity and impressive efficiency for the synthesis of HMF from glucose. The optimal conditions to obtain the best HMF yield (62.45%) were 0.2 M HCl and 0.1 M NaCl at 140 °C with a residence time of 60 minutes. An 18.22% molar yield of LA was obtained as a by-product. The effect of different anions was also investigated, and it was determined that not only the hydrogen ions, but also the nature of the acid and the type of salt played a joint role in improving the HMF yield. In addition, a possible synthesis pathway was proposed for large scale production of HMF.

A novel solid p-hydroxybenzenesulfonic acid–formaldehyde resin (SPFR) was prepared via a straightforward hydrothermal method. The catalytic properties of SPFR solid acids were evaluated in the dehydration reaction of fructose and glucose to 5-hydroxymethylfurfural (HMF). SEM, TEM, N2 adsorption–desorption, elemental analysis (EA), thermogravimetric analysis (TGA), and FT-IR were used to explore the effects of catalyst structure and composition on the HMF preparation from fructose. The effects of reaction time and temperature on the dehydration of fructose and glucose were also investigated. An HMF yield as high as 82.6% was achieved from fructose at 140 °C after 30 min, and 33.0% was achieved from glucose at 190 °C in 30 min. Furthermore, the recyclability of SPFR for the HMF production from fructose in 5 cycles was good.

The solid, super, acid catalyst S2O82−/ZrO2–TiO2–SiO2, which has both a strong Bronsted acid and Lewis acid, was prepared and applied in lignin depolymerization. The results indicate that S2O82−/ZrO2–TiO2–SiO2 is an effective catalyst for lignin depolymerisation since the liquid product was almost completely dissolved in ethyl acetate, indicating that it was comprised of mostly oligomeric lignin degradation products. The effect of hydrogenation co-catalysts (Pd/C, Pt/C and Ru/C, Rh/C) were also studied and found to improve the yield of aromatic compounds and the petroleum ether soluble fraction, which are mostly monomeric and dimeric products. The resulting yields of aromatic compounds and petroleum ether soluble products were 14.8% and 46%, respectively, when S2O82−/ZrO2–TiO2–SiO2 and Pt/C mixed catalyst was used at 310 °C for 24 hours. These results show that the use of a combination Bronsted and Lewis acid catalyst in combination with a hydrogenation catalyst (S2O82−/ZrO2–TiO2–SiO2 together with a noble metal catalyst) opens a practical route for efficient lignin depolymerization.

A resorcinol-formaldehyde resin carbon (RFC) catalyst with a well-developed, ordered, mesoporous framework was prepared using a soft template method at room temperature. The carbon was sulfonated in water using sulfanilic acid under mild atmospheric conditions. The sulfonated RFC (S-RFC) was characterized by N2 adsorption–desorption, elemental analysis, TEM, XPS, and FT-IR. It was determined that S-RFC is an efficient solid acid catalyst for furfural production from xylose and corn stover in γ-valerolactone (GVL). The effects of reaction time, reaction temperature, catalyst loading, substrate dosage and water concentration were investigated. 80% furfural yield and 100% xylose conversion were obtained from xylose at 170 °C in 15 min with 0.5 g catalyst. Comparatively, 68.6% furfural yield was achieved from corn stover at 200 °C in 100 min when using 0.6 g catalyst. Since there was no discernable decrease in furfural yield after multiple conversions utilizing the same catalyst, the recyclability of the catalyst is considered good.

A two-stage pretreatment method was developed to improve sugar recovery in this study. Firstly, the corn stover was pretreated with acidic dioxane to remove lignin, then the residue was subjected to dilute hydrochloric acid to eliminate the negative effects of hemicelluloses on enzymatic hydrolysis as well as increasing xylose yield. The optimal condition was 90 °C, 20 min, and 9/1 (v/v) dioxane–water including 1.0 wt% HCl solution in the first stage followed by 120 °C and 40 min for 1.0 wt% dilute hydrochloric acid in the second stage. The total yields of glucose and xylose were 91.5% and 79.7%, respectively, with a low cellulase dosage of 3 FPU g−1 of substrate. This two-stage pretreatment was effective due to the removal of lignin in the first stage and the hydrolysis of hemicelluloses in the second stage, resulting in a very high sugar recovery with a low enzyme loading.

The value-added utilizations of technical lignin are restricted by its heterogeneous features, such as high polydispersity, complex functional group distribution, ununiformed reactivity, etc. Fractionation of lignin into more homogeneous parts represents a promising approach to overcome this challenge. In the present study, softwood kraft lignin was fractionated into four different portions (F1, F2, F3, and F4) by first dissolving it in a methanol–acetone mixture followed by sequential precipitation with various organic solvents (ethyl acetate, 1:1 ethyl acetate/petroleum ether, petroleum ether) of decreasing solubility parameters. The yields of various fractions F1, F2, F3, and F4 were 48%, 39%, 10%, and 3%, respectively. The results from gel permeation chromatography indicated that the molecular weights of each fraction decreased from F1 to F4. The lowest molecular weight fraction F4 contained mainly monomeric and dimeric aromatic structures such as guaiacol and vanillin formed from lignin degradation. ...

Many biorefineries have not been commercialized due to poor economic returns from final products. In this work, a novel process has been developed to coproduce valuable sugars, xylo-oligosaccharides, and lignosulfonates from hardwood. The modified process includes a mild autohydrolysis pretreatment, which enables for the recovery of the xylo-oligosaccharides in auto-hydrolysate. Following enzymatic hydrolysis, the residue is sulfomethylated to produce lignosulfonates. Recycling the sulfomethylation residues increased both the glucan recovery and lignosulfonate production. The glucose recovery was increased from 81.7% to 87.9%. Steady state simulation using 100g of hardwood produced 46.7g sugars, 5.9g xylo-oligosaccharides, and 25.7g lignosulfonates, which were significantly higher than that produced from the no-recycling process with 39.1g sugars, 5.9g xylo-oligosaccharides, and 15.0g lignosulfonates. The results indicate that this novel biorefinery process can improve the production of fermentable sugars and lignosulfonate from hardwood as compared to a conventional biorefinery process.

BioChoice lignin (BCL) is a newly commercialized pine kraft lignin from Plymouth Mill of Domtar, which is precipitated from black liquor of bleachable-grade pulp. Indulin AT is a pine kraft lignin commercialized by Meadwestvaco for the past 60 years, which is precipitated from black liquor of linerboard-grade pulp. Thus, the two technical lignins are produced under quite different conditions in terms of alkali charge and pulping time/temperature. While the chemical structure of Indulin AT is well documented, that of BCL is totally unknown. In this study, chemical structures of BCL and Indulin AT are characterized using modern analytical techniques and compared with those of pine milled wood lignin (MWL) in order to elucidate the structural changes that occur during kraft pulping and the structural differences, if any, between BCL and Indulin AT. Both BCL and Indulin AT are structurally very different from the native lignin (MWL) in wood, indicating drastic structural modification during the kraft pulping ...

A novel integrated process to coproduce bioethanol and lignosulfonate from bamboo residues was investigated. Explicitly, the fermentable sugars (glucose and xylose) were saccharified from the kraft pulped bamboo residues with 12 % effective alkaline charge, followed by a sequential fermentation strategy was applied to produce bio-ethanol from these fermentable sugars. The kraft lignin (KL) generated in pulping process and the enzymatic hydrolysis residues (EHR) were sulfomethylated to produce lignosulfonate. Results showed that 229.8 g of KL, 495.6 g of fermentable sugars (368.7 g glucose and 126.9 g xylose) and 103.6 g of EHR were generated from 1000 g bamboo residues after consequent processes of kraft pulping and enzymatic hydrolysis, respectively. Under optimal conditions of fermentation and sulfomethylation, 1000 g bamboo residues could produce 201.4 g of ethanol (158.7 g from glucose and 42.7 g from xylose) and 234.9 g of pure lignosulfonate (197.6 g from KL and 37.3 g from EHR) from 1000 g bamboo residues. This integrated process may potential be an economically profitable for the biorefinery of bamboo residues.

Selective conversion of biomass-derived carbohydrates into 5-hydroxy-methylfurfural (HMF) is of great significance for biomass conversion. In this study, a novel solid Bronsted acid was prepared simply by the copolymerization of paraformaldehyde and p-toluenesulfonic acid and then used to catalyze the conversion of various carbohydrates into HMF in γ-valerolactone-water (GVL/H2O) reaction medium for the first time. The catalyst exhibited strong acidity, good water resistance, and high thermal stability. The present work focuses on the effects of various reaction parameters, including reaction temperature, time, water concentration, solvent, fructose level, and catalyst loading, on fructose dehydration. The catalyst exhibited excellent catalytic performance for HMF production from fructose in GVL and furnished a high HMF yield of 78.1% at 130 °C in 30 min. The recycling experiments suggested that the solid acid catalyst could be recycled at least seven times without a noticeable decrease in the catalytic activity. In addition, an attempt to study the one-step conversion of sucrose, glucose, and cellulose into HMF and furfural was performed using the same catalytic system.

Effects of a photocatalyst, C60-modified Bi2TiO4F2, on pine kraft lignin under visible light irradiation were investigated, along with those of Bi2TiO4F2 and C60/TiO2 as references. The influences of pH, C60 mass fraction, and the initial lignin concentration on lignin conversion and yields of mono-phenolic products were investigated. Seven products were determined by GC/MS, including phenol, 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, vanillin, acetovanillone, and homovanillic acid. The yields of products and lignin conversion were higher by C60/Bi2TiO4F2 than Bi2TiO4F2 and C60/TiO2. C60/Bi2TiO4F2 and C60/TiO2 were more stable than Bi2TiO4F2 upon repetitive recycling of catalyst. The effectiveness of C60/Bi2TiO4F2 declines 25%, whereas that of Bi2TiO4F2 declines 56.4% after being recycled five times. FTIR and HRTEM indicated that the deactivation of photocatalysts might be caused by lignin adsorbed on the surface of photocatalysts and the change in the crystal structure.

Recent techno-economic studies of proposed lignocellulosic biorefineries have concluded that creating value from lignin will assist realization of biomass utilization into valuable fuels, chemicals, and materials due to co-valorization and the new revenues beyond carbohydrates. The pretreatment step within a biorefinery process is essential for recovering carbohydrates, but different techniques and intensities have a variety of effects on lignin. Acidic and alkaline pretreatments have been shown to produce diverse lignins based on delignification chemistry. The valorization potential of pretreated lignin is affected by its chemical structure, which is known to degrade, including inter-lignin condensation under high-severity pretreatment. Co-valorization of lignin and carbohydrates will require dampening of pretreatment intensities to avoid such effects, in spite of tradeoffs in carbohydrate production.

P-toluene sulfonic acid (PTSA) was utilized to pretreat corn stover. Changes in morphology and structure of untreated and pretreated samples were analyzed by ESEM, TEM, BET, XRD and SXT. The characterization results demonstrated that PTSA pretreatment could markedly improve cellulase accessibility to cellulose because of the removal of lignin and hemicellulose simultaneously. The maximum glucose yield (67.2%) with an enzyme loading of 5FPU•g−1 substrate was achieved after the sample was the pretreated at 80 °C for 10 min with 71.0 wt% PTSA. P-toluene sulfonic acid pretreatment was a valid method to improve the enzymatic hydrolysis performance of cellulose in corn stover at low reaction temperature with a short reaction time.

Kraft lignin depolymerization to liquid fuels with high yields is crucial to the comprehensive achievement of sustainable and economic feasibility. Herein, we prepared a bimetallic Co-Zn/Off-Al H-beta catalyst through a two-step post synthesis method composed of dealumination and metal incorporation. The bifunctional Co-Zn/Off-Al H-beta catalyst efficiently converted Kraft lignin to liquid fuels, which was attributable to the synergistic effect of Co hydrogen binding sites and Zn Lewis acid sites on H-beta support. Catalytic hydrogenation with Co:Zn = 1:3/Off-Al H-beta catalyst at 320 °C for 24 h gave the highest yield of petroleum ether soluble product (81%, mainly monomers and dimers). Under these conditions, the liquefied lignin gave a higher heating value of 33.3 MJ/kg, which is a significant increase from 26.0 MJ/kg of Kraft lignin. The catalyst stability test showed excellent recyclability. This work provides a paradigm of improving lignin depolymerization efficiency via the combined use of Lewis acid and hydrogenation catalyst.

A multi-omics quantitative integrative analysis of lignin biosynthesis can advance the strategic engineering of wood for timber, pulp, and biofuels. Lignin is polymerized from three monomers (monolignols) produced by a grid-like pathway. The pathway in wood formation of Populus trichocarpa has at least 21 genes, encoding enzymes that mediate 37 reactions on 24 metabolites, leading to lignin and affecting wood properties. We perturb these 21 pathway genes and integrate transcriptomic, proteomic, fluxomic and phenomic data from 221 lines selected from ~2000 transgenics (6-month-old). The integrative analysis estimates how changing expression of pathway gene or gene combination affects protein abundance, metabolic-flux, metabolite concentrations, and 25 wood traits, including lignin, tree-growth, density, strength, and saccharification. The analysis then predicts improvements in any of these 25 traits individually or in combinations, through engineering expression of specific monolignol genes. The analysis may lead to greater understanding of other pathways for improved growth and adaptation., A systematic analysis of lignin biosynthetic genes to quantitatively understand their effect on wood properties is still lacking. Here, the authors integrate transcriptomic, proteomic, fluxomic and phenomic data to quantify the impact of perturbations of transcript abundance on lignin biosynthesis and wood properties.

Milled wood lignins from alkaline pretreated wood with very low sugar content and a wide range of syringyl-to-guaiacyl (S/G) ratio between 1.2 and 3.0 were isolated from 12 industrially valuable hardwood (HW) species. The lignin preparations were investigated by means of a comprehensive 13C nuclear magnetic resonance (NMR) methodology to address the possibilities and limitations of this approach for HW native lignins and to estimate the structural variations within HW lignins. Good correlations were found for different independent methods for the quantification of major lignin moieties. The results were reliable at the C6 level and not only for relative comparison. The correlation was good between methoxyl group determinations by wet chemistry and those by 13C NMR spectroscopy. The limitations of the 13C NMR method were also pointed out. The differences in the S/G ratios can be large, but other structural deviations are less significant. Strong correlations between the S/G ratios and the amounts of other structural peculiarities could not be found by the 13C NMR approach. However, with increasing S/G ratios, the β-O-4 content showed increasing tendencies and the degree of condensation showed decreasing tendencies.

The best known and clearly very important lignin-degrading microorganisms are wood-degrading fungi causing “white rots”. Lignin may be converted into humus and slowly biodegraded in soil. Unlike cellulose and other carbohydrates, lignin is resistant to degradation by most microorganisms. Consequently, the lignin-degrading system of these fungi is very likely a complex of different enzymes. One approach to elucidating the chemistry of lignin degradation by white-rot fungi is to characterize the partially degraded polymer. This would reflect the microbially induced changes in lignin and point to the kind of catabolic reactions involved. Heavily degraded lignins were isolated from spruce wood decayed by white-rot fungi. Changes in lignin in wood at any given time during decay are limited to only a small portion of the total lignin and the bulk of the lignin remains structurally unchanged. Many degradative reactions of lignin have been employed for the characterization of lignin.

The impact of field-grown transgenic trees on wood characteristics and enzymatic saccharification was evaluated. Genes 4CL and CAld5H were down regulated or overexpressed to modify the lignin content or structure (S/V ratio) on black cottonwood (Populus trichocarpa Nisqually-1). These transgenic trees were grown in the real environment and evaluated after 2 and 3 years. The results exhibited that the lignin content for most of the transgenic black cottonwoods increased compared to their initial lignin content when grown inside the greenhouse. The lignin contents approached those of the wild types. Acid and green-liquor pretreatments were applied to the transgenic wood saw dust samples. Cellulase mediated saccharifications were then conducted for the pretreated and untreated samples. Sugar yield and carbohydrate saccharification efficiency of the enzymatic saccharification for most of the transgenic trees were observed to be higher than those of the wild types even though their lignin contents became similar.

Cadium sulfide/titanium dioxide (CdS/TiO2) catalyst was prepared by two different methods: microemulsion-mediated solvothermal hydrolyzation (CdS/TiO2 (SH)) and in-situ sulfurization under supercritical conditions (CdS/TiO2 (SS)). The photocatalysts were characterized by nitrogen adsorption-desorption, X-ray diffraction, X-ray photoelectron spectra, UV-Vis absorption spectra, and PL spectra. Photodegradation reactions of three monomeric and one dimeric lignin model compounds, and kraft pine lignin (Indulin AT) were carried out at room temperature in a weak alkaline aqueous system by visible light irradiation with air bubbling. Quantitative results showed that these lignin model compounds and kraft lignin were effectively degraded. While both phenolic and non-phenolic lignin units are reactive, the phenolic units appeared to react faster and preferentially reacted.

Biomass hydrolysate from autohydrolysis pretreatment was used for furfural production considering it is in rich of xylose, xylo-oligomers, and other decomposition products from hemicellulose structure. By using the vapor-releasing reactor system, furfural was protected from degradation by separating it from the reaction media. The maximum furfural yield of 73% was achieved at 200 °C for biomass hydrolysate without the use of the catalyst. This is because the presence of organic acids such as acetic acid in hydrolysate functioned as a catalyst. According to the results in this study, biomass hydrolysate with a vapor-releasing system proves to be efficient for furfural production. The biorefinery process which allows the separation of xylose-rich autohydrolysate from other parts from biomass feedstock also improves the overall application of the biomass.

Fed-batch method has shown a great promise in debottlenecking the high-solid enzymatic hydrolysis for the commercialization of cellulosic biosugar conversion for biofuel/biochemical production. To further improve enzymatic hydrolysis efficiency at high solid loading, fed-batch methods of green liquor-pretreated hardwood were performed to evaluate their effects on sugar recovery by comparing with one-stage batch method in this study. Among all the explored conditions, the fed-batch at 15% consistency gave higher sugar recovery on green liquor-pretreated hardwood compared to that of one-stage batch. By using general linear model analysis, the percentage of enzymatic sugar recovery in fed-batch consistency method (increasing consistency from the initial 10.7 to 15% at intervals of 24 and 48 h) was higher than that of batch hydrolysis at higher density of 15% consistency. Under that best fed-batch condition, the total sugar recovery of pretreated hardwood in enzymatic hydrolysate reached approximately 48.41% at Cellic® enzyme loading of 5 filter-paper unit (FPU)/g and 58.83% at Cellic® enzyme loading of 10 FPU/g with a hydrolysis time of 96 h.

With the aim to enhance the direct conversion of raw corn stover into furfural, a promising approach was proposed employing a novel heterogeneous strong acid catalyst (SC-CaCt-700) in different solvents. The novel catalyst was characterized by elemental analysis, N2 adsorption-desorption, FT-IR, XPS, TEM and SEM. The developed catalytic system demonstrated superior efficacy for furfural production from raw corn stover. The effects of reaction temperature, residence time, catalyst loading, substrate concentration and solvent were investigated and optimized. 93% furfural yield was obtained from 150mg corn stover at 200°C in 100min using 45mg catalyst in γ-valerolactone (GVL). In comparison, 51.5% furfural yield was achieved in aqueous media under the same conditions (200°C, 5h, and 45mg catalyst), which is of great industrial interest. Furfural was obtained from both hemicelluloses and cellulose in corn stover, which demonstrated a promising routine to make the full use of biomass.

In this study, a novel catalyst, S2O82--KNO3/TiO2, which has active acidic and basic sites, was prepared and used in lignin hydrocracking with a co-catalyst, Ru/C. Ru/C is an efficient hydrogenation catalyst and S2O82--KNO3/TiO2 is a dual catalyst, which could efficiently degrade lignin. This catalytic hydrogenation system can reduce solid products to less than 1%, while giving a high liquid product yield of 93%. Catalytic hydrocracking of kraft lignin at 320°C for 6h gave 93% liquid product with 0.5% solid product. Most of this liquid product was soluble in petroleum ether (60% of 93%), which is a clear liquid and comprises mainly of monomeric and dimeric degradation products. These results demonstrated that the combination of the two catalysts is an efficient catalyst for liquefaction of lignin, with little char formation (∼1%). This concept has the potential to produce valuable chemicals and fuels from lignin under moderate conditions.

A biologically-based lignocellulosic biorefinery process for obtaining carbohydrates from raw biomass was investigated across six diverse biomasses (three hardwoods & three nonwoods) for the purpose of decoding lignin's influence on sugar production. Acknowledging that lignin could positively alter the economics of an entire process if valorized appropriately, we sought to correlate the chemical properties of lignin within the process to the traditional metrics associated with carbohydrate production-cellulolytic digestibility and total sugar recovery. Based on raw carbohydrate, enzymatic recovery ranged from 40 to 64% w/w and total recovery ranged from 70 to 87% w/w. Using nitrobenzene oxidation to quantify non-condensed lignin structures, it was found that raw hardwoods bearing increasing non-condensed S/V ratios (2.5-5.1) render increasing total carbohydrate recovery from hardwood biomasses. This finding indicates that the chemical structure of hardwood lignin influences the investigated biorefinery process' ability to generate carbohydrates from a given raw hardwood feedstock.

Waste wheat straw (WWS) is the waste product from feedstock preparation process in a straw pulp mill. It has a significant annual production rate and no commercial value has been explored on this material. In this study, waste wheat straw was pretreated using an autohydrolysis process followed by mechanical refining, and the pretreated materials were further enzymatically hydrolyzed to evaluate the total sugar recovery for bioethanol production. Results show that autohydrolysis at 170 °C for 40 min followed by 6000 revolution PFI refining provided the best result in this study, where a total sugar recovery (total sugars in autohydrolysis filtrate and enzymatic hydrolyzate over total carbohydrates on raw WWS) of 70 % at 4 filter paper unit per oven dry gram (FPU/OD g) substrate enzyme charge could be obtained. The economic evaluation of this biorefinery process indicates that cellulosic ethanol production from autohydrolysis of WWS is a very profitable business, with 28.4 % of internal rate of return can be achieved based on current ethanol wholesale price in China.

The protocol of alkaline nitrobenzene oxidation was investigated to improve its ability to identify the different lignin structures for both woody and non-woody biomass. The survival factors of all six oxidation products—syringaldehde (Sr), vanillin (V), p-hydroxybenzaldehyde (B) and their corresponding acids, syringic acid (Sa), vanillic acid (Va), and p-hydroxybenzoic acid (Ba)—were studied at 170, 180, and 190°C for several residence times. Under similar conditions, various lignin model compounds—a softwood (loblolly pine), a hardwood (red maple), and a non-wood raw material (corn stover)—were oxidized. Molar yields of oxidation products were determined and the ratios of (Sr+Sa)/(V+Va), (Sr/V), and B/(V+Va) (B/V) were calculated. All oxidation products were relatively stable at 170 and 180°C but showed some degradation at 190°C, especially at long residence time. In all cases, p-hydroxybenzoic acid was barely detectable. While yields of oxidation products reach a maximum at 170°C for pine and maple, ma...

Hardwood lignin preparations were isolated using classical milled wood lignin (MWL) and cellulolytic enzyme lignin (CEL) protocols. Furthermore, we managed to produce a lignin preparation of a very high yield, above 90%, with high purity and minimal structural degradation. This was achieved by dissolution and regeneration of milled wood prior to enzymatic hydrolysis, along with the use of 80% dioxane for lignin extraction. This preparation (RCEL-80) yield was about 4.5 and 2.5 times higher than the yields of the traditional MWL and CEL preparations, correspondingly, at the same milling time. The preparations obtained were comprehensively analyzed with state-of-the-art quantitative NMR techniques and wet chemistry methods. CELs were representative preparations for hardwood lignins as the S/G ratios in the CELs were equivalent to those in lignin in situ. Degradation of the main lignin subunits was very low. Importantly, the structures of CELs were independent of the preparation yield and were very similar t...

Kraft pulping is one possible pretreatment for softwood to economically produce bioethanol. This work evaluates the techno-economic potential of using the kraft process for producing bioethanol from softwoods in a repurposed or co-located kraft mill. Pretreated loblolly pine was enzymatically hydrolyzed at low enzyme dosages of 5 and 10 FPU/g of substrate. Pretreated residue with 13% lignin content had the highest sugar recovery, 32.7% and 47.7% at 5 and 10 FPU/g, respectively. The pretreated residues were oxygen delignified and refined. In all cases, oxygen delignification improved sugar recovery, while refining was mostly effective for pulps with high lignin content. At 5 FPU/g, the sugar recovery for all kraft pulps was 51 to 53% with oxygen delignification and refining. Increasing the enzyme dosage to 10 FPU/g increased the sugar recovery for these pulps to greater than 60%. Economic analysis for the pulps with different initial lignin content showed that kraft pulps with an initial lignin content of 6.7% with oxygen delignification had an ethanol yield of 285 L/ODt wood and the lowest total production cost of $0.55/L. Pulps with initial lignin content of 18.6% had a total production cost of $0.64/L with an ethanol yield of 264 L/ODt wood.