Mikhail Iakovlev

Novel concepts of dissolving pulp production

Herein, we report about existing and novel dissolving pulp processes providing the basis for an advanced biorefinery. The SO2–ethanol–water (SEW) process has the potential to replace the acid sulphite process for the production of rayon-grade pulps owing to a higher flexibility in the selection of the raw material source, substantially lower cooking times, and the near absence of sugar degradation products. Special attention is paid to developments that target toward the selective and quantitative fractionation of paper-grade pulps into hemicelluloses and cellulose of highest purity. This target has been accomplished by the IONCELL process where the entire hemicellulose fraction is selectively dissolved in an ionic liquid in which the H-bond basicity and acidity are adequately adjusted by the addition of a co-solvent. At the same time, pure hemicellulose can be recovered by further addition of the co-solvent, which then acts as a non-solvent. The residual pure cellulose fraction may then enter a Lyocell process for the production of regenerated cellulose products.

Separation of Hemicellulose and Cellulose from Wood Pulp by Means of Ionic Liquid/Cosolvent Systems

Pulp of high cellulose content, also known as dissolving pulp, is needed for many purposes, including the production of cellulosic fibers and films. Paper-grade pulp, which is rich in hemicellulose, could be a cheap source but must be refined. Hitherto, hemicellulose extraction procedures suffered from a loss of cellulose and the non-recoverability of unaltered hemicelluloses. Herein, an environmentally benign fractionation concept is presented, using mixtures of a cosolvent (water, ethanol, or acetone) and the cellulose dissolving ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIM OAc). This cosolvent addition was monitored using Kamlet-Taft parameters, and appropriate stirring conditions (3 h at 60 °C) were maintained. This allowed the fractionation of a paper-grade kraft pulp into a separated cellulose and a regenerated hemicellulose fraction. Both of these exhibited high levels of purity, without any yield losses or depolymerization. Thus, this process represents an ecologically and economically efficient alternative in producing dissolving pulp of highest purity.

Efficient Fractionation of Spruce by SO2-Ethanol-Water Treatment: Closed Mass Balances for Carbohydrates and Sulfur

SO(2)-ethanol-water (SEW) lignocellulosic fractionation has the potential to overcome the present techno-economic barriers that hinder the commercial implementation of renewable transportation fuel production. In this study, SEW fractionation of spruce wood chips is examined for its ability to separate the main wood components, hemicelluloses, lignin, and cellulose, and the potential to recover SO(2) and ethanol from the spent fractionation liquid. Therefore, overall sulfur and carbohydrate mass balances are established. 95-97 % of the charged SO(2) remains in the liquid and can be fully recovered by distillation. During fractionation, hemicelluloses and lignin are effectively dissolved, whereas cellulose is preserved in the solid (fibre) phase. Hemicelluloses are hydrolysed, producing up to 50 % monomeric sugars, whereas dehydration and oxidation of carbohydrates are insignificant. The latter is proven by the closed carbohydrate material balances as well as by the near absence of corresponding by-products (furfural, hydroxymethylfurfural (HMF) and aldonic acids). In addition, acid methanolysis/GC and acid hydrolysis/high performance anion exchange chromatography (HPAEC) methods for the carbohydrate determination are compared.

Kinetics of fractionation by SO2–ethanol–water (SEW) treatment: understanding the deconstruction of spruce wood chips

The kinetics of SO2–ethanol–water (SEW) fractionation of spruce were studied using wood meal and chips and compared to those of SO2–water, acid sulfite (AS) and ethanol–acid sulfite treatment. The SEW lignin removal rate was found to be similar to that of AS at the same free SO2 concentration, while the lignin sulfonation rate is considerably higher for the acid sulfite systems. No relation between acidity and sulfonation rate was observed putting into question the acid-catalysed nature of this reaction. The observed SEW sulfonation and delignification patterns are consistent with Hagglunds “fast sulfonation–slow hydrolysis” consecutive scheme. The data indicate that during the initial phase hemicelluloses are removed together with lignin as lignocarbohydrate complexes, while cellulose is protected from hydrolytic attack by lignin leading to a lower hydrolysis rate. The SEW hemicellulose dissolution behaviour can be understood by the low tendency of glucomannan to “crystallise” onto cellulose. The understanding of the dissolution pattern of lignin and hemicellulose may help to interpret the enzymatic hydrolysis behaviour of SEW residual solids subjected to different degree of fractionation.

Kinetics of SO2-ethanol-water pulping of spruce 10th EWLP, Stockholm, Sweden, August 25–28, 2008

Abstract 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.

Conditioning of SO2-ethanol-water spent liquor from spruce for the production of chemicals by ABE fermentation.

Abstract The objective of this study is to develop a process for conditioning spent liquor produced by SO2-ethanol-water (SEW) fractionation of spruce wood chips for fermentation to butanol, ethanol and acetone/isopropanol, i.e., by means of the so called acetone-butanol-ethanol (ABE) process using Clostridia bacteria. This study serves as part of an overall project aiming at the development of economic processes for producing chemicals and biofuels from mixed forest biomass via SEW fractionation and ABE fermentation technologies.

SO2-Ethanol-Water (SEW) Pulping: II. Kinetics for Spruce, Beech, and Wheat Straw

Abstract SO2-ethanol-water (SEW) delignification kinetics for spruce, beech, and wheat straw are presented. All these species produce pulps using SEW cooking liquor and follow first order delignification kinetics at similar bulk delignification rates. However, residual delignification is much slower for beech than for spruce. The hemicelluloses retention (135°C) and cellulose degradation kinetics are also characterized for beech SEW pulping. Xylan and glucomannan are removed from the pulp following first-order kinetics with a higher rate constant for xylan. Cellulose is retained in the fibers until kappa number 9, after which it starts to dissolve in the liquor. The yield also drops significantly in the region of kappa numbers 9–7. Cellulose degradation is followed by intrinsic viscosity measurements and is found to be zero order in cellulose. The rates are higher at 135 and 145°C for beech SEW pulping than for spruce.

SO2-Ethanol-Water (SEW) Pulping: I. Lignin Determination in Pulps and Liquors

Abstract 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.

SO2–ethanol–water (SEW) fractionation of spruce: kinetics and conditions for paper and viscose-grade dissolving pulps

The study describes SO2–ethanol–water fractionation of spruce as a promising basis for future Biorefineries. The dissolution kinetics of lignin and hemicelluloses as well as the depolymerisation kinetics of cellulose during the fractionation process are expressed in terms of the H-factor, a parameter combining fractionation temperature and duration. The raw material moisture content is shown to have a very small effect on the fractionation kinetics. The liquor-to-wood ratio has little effect on the process during the (delignification) bulk phase, while in the residual phase the effect becomes pronounced. During the latter phase, lower liquor-to-wood ratios lead to higher residual lignin content, lower residual hemicelluloses and pulp viscosity, but higher hemicelluloses removal selectivity. Higher delignification rates and selectivities are obtained at ethanol-to-water ratios close to 1 : 1 (w/w) and high SO2 concentrations (≥12 w/w%). Based on the presented data, the optimum fractionation conditions for the production of paper and viscose-grade dissolving pulps are quantified.

Effects of residual lignin and heteropolysaccharides on the bioconversion of softwood lignocellulose nanofibrils obtained by SO2-ethanol-water fractionation.

The amount of residual lignin and hemicelluloses in softwood fibers was systematically varied by SO2-ethanol-water fractionation for integrated biorefinery with nanomaterial and biofuel production. On the basis of their low energy demand in mechanical processing, the fibers were deconstructed to lignocellulose nanofibrils (LCNF) and used as substrate for bioconversion. The effect of LCNF composition on saccharification via multicomponent enzymes was investigated at different loadings. LCNF digestibility was compared with the enzyme activity measured with a quartz crystal microbalance. LCNF hydrolysis rate gradually decreased with lignin and hemicellulose concentration, both of which limited enzyme accessibility. Enzyme inhibition resulted from non-productive binding of proteins onto lignin. Near complete LCNF hydrolysis was achieved, even at high lignin and hemicellulose content. Sugar yields for LCNF were higher than those for precursor SEW fibers, highlighting the benefits of high surface area in LCNF.