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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...

The present study characterized effluents from the O, D0, and E stages using nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques to better understand the chemical nature of the dissolved organics formed from the bleaching of a high-yield hardwood kraft pulp. Understanding the structures and molecular weight distribution of these organics is the first step in developing methods to mitigate these contaminates in the discharged effluents. The results indicated that the molecular weight distribution (MWD) of the dissolved organics from oxygen delignification effluent is broader than those from D0 and E stage effluents. In addition, the O stage filtrate contained considerable amounts of lignin and xylan fragments, which showed its efficiency in removing such materials. The effluent from the D0 stage contained a lower amount of high molecular weight fragments and a higher amount of low molecular weight fragments versus the O-stage filtrate. Aromatic structures were nearly absent in the D0 stage filtrate, but the degraded organic material, presumably from oxidized lignin, contained olefinic (C=C) and carbonyl (C=O) functional groups. Furthermore, higher molecular weight fragments were detected in the E-stage effluent, presumably due to the extensive solubilization and removal of the oxidized lignin generated from the D0 pulp.

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 objective of this study was to evaluate the possibility of producing dissolving grade pulp from tobacco stalk through combining SO2-ethanol-water (SEW) fractionation, alkaline extraction, and bleaching with oxygen (O), chlorine dioxide (D), alkaline extraction with hydrogen peroxide (Ep), and hydrogen peroxide (P) (OD0(Ep)D1P). The results showed that the optimum SEW cooking condition to remove the original xylan and lignin in tobacco stalk to an acceptable level was 6% SO2 charge (by weight) at 135 °C for 180 min. A bleachable pulp (Kappa number of 21.5) was produced from the SEW-treated tobacco stalk via a subsequent 1% NaOH extraction. After the OD0(Ep)D1P sequence bleaching, the bleached pulp showed a high brightness (88.1% ISO) and a high α-cellulose content (94.9%). The viscosity (15.8 cP) and the residual xylan content (4.4%) of the pulp were within acceptable levels for dissolving pulp production. Thus, tobacco stalk was shown to be a viable raw material for dissolving pulp production following a SEW treatment, alkaline extraction, and a conventional bleaching sequence.

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...

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...

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.

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.