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Sugar maple (Acer saccharum) wood chips were pretreated with aqueous sodium hydroxide, sodium borohydride, and hydrogen peroxide pretreatments, and the characterization (i.e., amount, molar masses, and molar mass distributions) of the lignin dissolved during the pretreatments was performed. Of the applied pretreatments, especially borohydride pretreatments were efficient in dissolving lignin from this feedstock, as 20% to 28% of the dissolved organics were found to consist of dissolved lignin, contributing to 3.4% to 9.0% of the initial wood lignin. Corresponding values for 2.5% and 5.0% alkaline peroxide pretreatments were from 5.9% to 9.2% dissolved lignin of the total dissolved organics and from 1.1% to 3.2% of the initial wood lignin. Additionally, determined molar masses and molar mass distributions indicated that borohydride pretreatments generally led to the formation of smaller-molar-mass lignin fragments when compared to reference pretreatments and to pretreatments conducted with alkaline peroxide process, indicating more efficient lignin degradation caused by borohydride addition. For example, Mn and Mw values of the analyzed reference effluents were 54%-62% and 66%-71% higher when compared to the corresponding borohydride effluents, respectively. [ABSTRACT FROM AUTHOR]

The objective of this work was to determine the effect of sodium methyl mercaptide (SMM) on the yield of the packaging-grade kraft pulp. Based on our experience with bleachable grade kraft pulping using SMM, only a co-addition of 4.38% SMM with white liquor was studied. The cooking temperature and H-factor were adjusted to reach the target kappa number. The experimental results showed about a 2.7% (on O.D. (oven dry) wood basis) increase in the pulp yield after the co-addition of 4.38% SMM (on O.D. wood basis). The use of 4.38% SMM allowed lowering of the severity of the following process variables: the white liquor effective alkali charge (EA, on O.D. wood basis) by 2.4%, the cooking temperature from 165 °C to 157 0C, and the H-factor from 535 to 295. For 98 kappa pulp, the increase in pulp yield was mostly due to the increased retention of xylan (1.63%, on wood basis) and lignin (1.71%). The retention of galactoglucomannan was negligible (0.26%). There was a minor loss of cellulose (0.70%). The increase in the pulp yield in the presence of SMM can be explained by two non-exclusive mechanisms: stabilization of carbohydrate-reducing end groups during impregnation, and faster delignification during the bulk cooking phase. Based on the experimental data, we presently do not know which of the two mechanisms for increasing the pulp yield is dominating. [ABSTRACT FROM AUTHOR]

Using a Berty-type CSTR reactor, Ji (2007. Kinetics and mechanism of oxygen delignification, Ph.D. thesis. The University of Maine) obtained oxygen delignification kinetics first order in lignin when neglecting the higher initial delignification phase. In the present study the same Berty/CSTR reactor with an improved temperature control was used to determine the oxygen delignification kinetics of Southern Pine kraft pulp, with the kinetics now corrected for lignin removed by oxygen-free alkaline leaching. This removes the initial high delignification rate peak so that the kinetics over the entire lignin range can be modelled as first order in "reactive" lignin, which is lignin corrected for a small amount of unreactive lignin. It suggests that softwood pulp oxygen delignification consists of two contributions; phenolic delignification and alkaline leaching. The initial alkaline leaching phase is mathematically described by semi-infinite alkaline diffusion of dissolved lignin trapped in the cell wall after pulp washing. For phenolic delignification, the reaction orders in alkali concentration and oxygen of the power law delignification equation are 0.3 and 0.44 respectively, while the activation energy is 63 kJ/mol. Taking into account the unreactive HexA, the small amount of unreactive lignin, and the lignin removed by alkaline leaching, the kappa number is well predicted by the new delignification kinetics. [ABSTRACT FROM AUTHOR]

Sugarcane straw (SCS) lignin is extracted by SO 2 -Alcohol-Water (SAW) fractionation (155 °C, 1 h) using methanol, ethanol or isopropanol as pulping solvent (SO 2 /Alcohol/Water = 12/44/44 wt%). The SAW fractionation removes 90–95% lignin from SCS of which only 30–45% is isolated as precipitated lignin after solvent evaporation. The precipitated and pulp residual lignin (5–10%) are analyzed for their degree of sulfonation (S/C9) while precipitated lignin is further analyzed in terms of molecular weight distribution (MWD) and alkoxylation reactions. Similar S/C9 values for methanol, ethanol and isopropanol lignin show that the degree of sulfonation is independent of fractionation solvent. However, the sulfonated lignin is comparatively less soluble in the methanol-based liquor compared to the corresponding lignins in the ethanol- and isopropanol-based liquors. The mass average molecular weight, M w , is highest for isopropanol lignin (∼3800) while the numbers for methanol and ethanol lignins are comparatively smaller but nearly equal in magnitude (∼3000). Alkoxyl groups and nuclear magnetic resonance (NMR) analyses are performed to interpret the differences in lignin M w and alkoxylation reactions. Different ether and ester type linkages are identified in NMR spectra confirming lignin alkoxylation. Lignin carbohydrate complexes (LCC) are also found in NMR spectra confirming that some of the detected carbohydrates are covalently bound to lignin. [ABSTRACT FROM AUTHOR]

Wheat straw was pretreated at 150 °C for 100 min at a liquor-to-straw ratio of 6 L/kg (oven dry basis) straw using aqueous formic acid (FA) concentrations ranging from 0 to 15 g/L. The results showed excellent sugar and lignin mass balances for pretreatment, and precipitated lignin in the hydrolysate obtained at 15 g/L of FA decreased to 0.31 g/100 g straw compared to autohydrolysis (no FA) of 0.94 g/100 g straw. The average molecular weight of precipitated lignin decreased from 1970 g/mole for autohydrolysis to 710 g/mole at 15 g/L of FA. The monomeric sugar yield during pretreatment improved from 3.83 g/100 g for autohydrolysis to 23.5 g/100 g at 15 g/L FA. [ABSTRACT FROM AUTHOR]

Quantitative determination of lignin in SO2-ethanol-water (SEW) pulps and spent liquors is described. The methods developed for conventional sulfite pulping are successfully applied to the SEW process. Linear correlations between Klason/total lignin content and kappa number are found over a wide pulp yield range for spruce, beech, and wheat straw. Lignin content of the spruce spent SEW liquors is determined using either hydrogen peroxide to remove SO2 and dilution by 3% sulfuric acid or simply by dilution with 0.1M sodium hydroxide. The recommended wavelength is 280 nm. The experimentally found values for the extinction coefficient of dissolved lignin in 3% sulfuric acid and in 0.1M NaOH are 19 and 23 L/(g·cm), respectively. The interference of furanic compounds is eliminated by reduction with sodium borohydride. [ABSTRACT FROM AUTHOR]

Abstract: In order to utilize hemicelluloses from biomass as a feedstock for production of higher value added products such as biofuels and bio-based chemicals, it is essential to assess the chemical composition of the liquid phase and molecular weight distribution of isolated carbohydrates. The association of hemicelluloses with lignin also plays an important role for utilization of isolated hemicelluloses. In the present study carbohydrates were first extracted from a mixture of southern hardwoods by autohydrolysis at different temperatures for 100min, and then precipitated after mixing with four volumes of ethanol. Depending on the temperature, all (100% at 130°C) or a small part (5% at 170°C) of the oligomeric hemicelluloses present in the extract precipitated together with some lignin and oligo-glucose (glucans). The classical iodine test confirmed that most of the glucans are actually starch. Oligo-glucose is the major component in the precipitate from extracts produced at 150°C and below, while xylan is the main component at 160°C. Almost all lignin in the precipitate is in the form of lignin–carbohydrate complexes. The average M w of the carbohydrates isolated from the extract decreases with increasing autohydrolysis temperature. The average DP of hemicelluloses isolated from the extract decreases from about 71 to 36 over the temperature range from 130 to 170°C during 100min autohydrolysis. [ABSTRACT FROM AUTHOR]

Lignin and ash material balances of SO 2 -ethanol–water (AVAP®) fractionation of sugarcane (SC) straw were thoroughly studied at various conditions. Most of straw lignin and ash dissolve in the liquor and 40–80% of lignin is precipitated after ethanol removal as a pure (∼99%) and sulfur-lean (<2%) fraction. Most of the acid-soluble ash and its elements (Na, K, Fe, Al) as well as large portion of silica are removed from the fiber phase. Straw lignin behavior exhibited differences compared to wood lignin including high apparent content in fiber, higher degree of sulfonation of dissolved lignin, and dense char-like precipitate formation upon ethanol removal. Variation in fractionation conditions did not have significant effect on lignin properties, while post-sulfonation was capable of changing its form from char-like to colloidal precipitate. [ABSTRACT FROM AUTHOR]

The sulfur balance of SO 2 -ethanol-water (AVAP®) fractionation of sugarcane (SC) straw was investigated. Hydrogen sulfite and sulfite anions are nearly absent in the liquors, despite cations present in straw, whose effect is thus limited to neutralization of lignosulfonic acids decreasing the acidity. Higher degree of sulfonation was observed for dissolved straw lignin compared to wood lignin (0.8–0.9 vs. 0.25 S/C9). Sulfur dioxide amounts of 0.9–1.2, 4.1–4.3 and 44–49 g per o.d. kg straw were bound to pulp, precipitated lignin and lignosulfonic acid, respectively, while the rest of SO 2 was recovered by distillation from the spent fractionation suspensions. [ABSTRACT FROM AUTHOR]

The overall target of this project, called Bioforest, is to develop an economic process for the production of commodity chemicals from mixed forest biomass, consisting of logging residues of hardwoods (HW) and softwoods (SW) and also from recycled fibers. The aim is to dissolve the biomass lignin and to produce monosugars based on hemicelluloses and hydrolyzed cellulose in high yield. The hydrolyzate could subsequently be converted into chemicals by modified acetone-butanol-ethanol fermentation. Here, the total mass balances of SO2-ethanol-water fractionation of different types of biomass feedstocks, such as SW and HW biomass, and deinked pulp are presented. Chemical composition of the feedstocks, solid residues (pulps) and spent liquors of fractionation were analyzed to gain more understanding about the fractionation procedure. The analysis was focused on carbohydrates, lignin, ash, acetyl groups and sugar degradation products. It was also examined if all feedstocks could be treated simultaneously in one digester because a larger feedstock supply within an economic transport radius improves the viability of the process. The fractionation approach was successful and it can be concluded that the method presented is very versatile for future applications in lignocellulosic biorefineries. [ABSTRACT FROM AUTHOR]

The "near neutral hemicellulose extraction process" involves extraction of hemicellulose using green liquor prior to kraft pulping. Ancillary unit operations include hydrolysis of the extracted carbohydrates using sulfuric acid, removal of extracted lignin, liquid-liquid extraction of acetic acid, liming followed by separation of gypsum, fermentation of C5 and C6 sugars, and upgrading the acetic acid and ethanol products by distillation. The process described here is a variant of the "near neutral hemicellulose extraction process" that uses the minimal amount of green liquor to maximize sugar production while still maintaining the strength quality of the final kraft pulp. Production rates vary between 2.4 to 6.6 million gallons per year of acetic acid and 1.0 and 5.6 million gallons per year of ethanol, depending upon the pulp production rate. The discounted cash flow rate of return for the process is a strong function of plant size, and the capital investment depends on the complexity of the process. For a 1,000 ton per day pulp mill, the production cost for ethanol was estimated to vary between $1.63 and $2.07/gallon, and for acetic acid between $1.98 and $2.75 per gallon depending upon the capital equipment requirements for the new process. To make the process economically attractive, for smaller mill sizes the processing must be simplified to facilitate reductions in capital cost. [ABSTRACT FROM AUTHOR]

SO2-ethanol-water (SEW) pulping is a promising fractionation process for lignocellulosics to produce pulp and value-added chemicals as a contribution to the concept of forest biorefinery. The presence of SO2 leads to dissolution of hemicelluloses in high yield mostly as monomeric sugars, while lignin becomes soluble through sulfonation. After lignin removal, the dissolved sugars may be used as feedstock for fermentation to ethanol or butanol. SEW pulping may be considered a hybrid between solvent pulping (organosolv pulping by solvolysis) and acid sulfite pulping. Absence of an inorganic base leads to simplification of the recovery cycle. Furthermore, alcohol increases the impregnation rate of dissolved SO2 into wood, so that a separate impregnation phase is not necessary. Also, the presence of SO2 allows cooking of softwoods, while ethanol pulping is limited to hardwoods. Thus, SEW pulping may be applied to a wide variety of lignocellulosics at lower temperatures and similar cooking times than those used in kraft pulping. In the present study, SEW pulping experiments were performed on spruce chips at cooking temperatures of 135–165°C with a 12% SO2 solution at a liquor-to-wood ratio of 6:1 l kg-1. The effect of cooking temperature and time on kappa number, yield, and intrinsic viscosity of the pulp was determined. Based on these results, the kinetics of delignification, hemicelluloses removal, and cellulose hydrolytic destruction were established. [ABSTRACT FROM AUTHOR]

Special oxygen delignification experiments were performed in a differentially operated continuous stirred tank reactor (CSTR). Because the dissolved oxygen and alkali concentrations in the reactor are constant, the rate of lignin removal may be determined from the dissolved lignin content in the outflow stream measured by UV absorption. The delignification kinetics were determined at different temperatures, oxygen pressures and caustic concentrations on softwood kraft pulps of different kappa numbers. The kinetics are first order in residual lignin content [hexenuronic acid (HexA) corrected], and follow a Langmuir-type behavior for adsorption of oxygen on the active aromatic lignin sites. The first order in residual lignin content implies that the active lignin sites are uniformly distributed and have the same reactivity. It is proposed that the active site is the 3 carbon of the aromatic ring, where oxygen reacts to form a hydroperoxide, with a p Ka of almost 2 units higher than that of phenolic lignin. The kinetics of phenolic delignification can be described by assuming that the reaction between adsorbed oxygen and carbon 3 of the aromatic ring is the rate determining step. Alternatively, the decomposition of the hydroperoxide anion is rate determining. Peeling delignification has been proposed as an additional delignification route by peeling of hemicelluloses which have lignin fragments covalently bound to them. It is shown that the impact of peeling delignification is relatively small and limited to the initial delignification phase. Finally, data are presented showing that radicals may provide an essential contribution to delignification by their removal of non-lignin and non-HexA oxidizable structures contributing to the kappa number. [ABSTRACT FROM AUTHOR]

Highlights: [•] Nanofibrils (LCNF) were produced from softwood after SEW fractionation. [•] The effect of lignin and hemicelluloses on LCNF bioconversion was elucidated. [•] Enzyme binding and activity on LCNF was monitored in situ by QCM-D. [•] Hydrolysis of SEW LCNF produce sugar yields higher than those of fibers. [•] SEW-based biorefinery may integrate nanomaterial and biofuel production. [Copyright &y& Elsevier]

Inthe current study, a simple two-step fractionation process was developedfor utilization of hardwood biomass without forming troublesome stickylignin condensation products. The four product streams generated area hemicellulose extract, a lignin extract, separated wood fibers (pulp)and wood fiber bundles (rejects). All four product streams can befurther utilized for production of transportation fuel, chemicals,and biomaterials. The optimum fractionation conditions for mixed southernhardwood chips are the following: extraction with 10 g/L formic acid(FA) at 160 °C for 90 min followed by extraction with 50% (w/w)EtOH at 80 °C for 90 min. The yield of pulp and reject fibersthat are produced from the FA and EtOH pre-extracted wood chips bymechanical action are 38% and 28%, respectively. Cellulose to glucoseconversion yield of the FA treated wood, as well as that of the finalpulp and fiber bundles by enzymes, are strongly improved comparedto that of the original hardwood chips. [ABSTRACT FROM AUTHOR]

Three lignins: Indulin AT, Lignoboost™, and Acetocell lignin, were characterized and pyrolyzed in a continuous-fed fast pyrolysis process. The physical and chemical properties of the lignins included chemical composition, heat content, ash, and water content. The distributed activation energy model (DAEM) was used to describe the pyrolysis of each lignin. Activation energy distributions of each lignin were quite different and generally covered a broad range of energies, typically found in lignins. Process yields for initial continuous-fed fast pyrolysis experiments are reported. Bio-oil yield was low, ranging from 16 to 22%. Under the fast pyrolysis conditions used, the Indulin AT and Lignoboost™ lignin yielded slightly more liquid product than the Acetocell lignin. Lignin kinetic parameters and chemical composition vary considerably and fast pyrolysis processes must be specified for each type of lignin. [ABSTRACT FROM AUTHOR]