Mechanistic Differences Between Kraft and Soda/AQ Pulping. Part 1: Results from Wood Chips and Pulps

Abstract

Soda pulping catalyzed by anthraquinone (AQ) or 2-methylanthraquinone (MAQ) can produce hardwood chemical pulps similar to kraft pulps in all respect but for bleachability. Results accumulated in our laboratory suggest that the residual lignin in pulps from anthraquinone catalyzed processes is less reactive toward bleaching chemicals than that in kraft pulps. Analyses of pulps by periodate and permanganate oxidations suggest that the residual lignin from the non-sulfur processes contained more condensed structures than kraft residual lignin. The low reactivity of these structures is believed to be responsible for the lower brightness of bleached soda-AQ (SAQ) pulps. Pulping and bleaching trials with hardwood chips demonstrated that shortening of the cooking time and/or increasing the alkalinity is one strategy for improving bleachability of SAQ pulps. When sugar maple (Acer saccharum) chips were SAQ cooked for 1.0 and 2.0 h at 165°C, the higher kappa number pulp produced after 1.0 h of cooking bleached to a significantly higher brightness with a small increase in the chlorine dioxide application.     

Sustainable Production of Levulinic Acid from the Cellulosic Fraction of Pinus Pinaster Wood: Operation in Aqueous Media Under Microwave Irradiation

The fractionation of the structural components of lignocellulosic biomass (cellulose, hemicelluloses, and lignin) and the separate utilization of the resulting fractions for specific purposes, according to the philosophy of biorefineries, enables the development of sustainable processes for biomass utilization. In this work, Pinus pinaster wood was subjected to aqueous processing to remove water-soluble extractives and hemicelluloses, and the resulting solid was subjected to pulping with HCl-catalyzed acetic acid solutions (Acetosolv method). The pulp was employed as a substrate for levulinic acid manufacture by reaction in acidic media under microwave irradiation. The effects of the major operational variables (temperature, reaction time, and acid concentration) on the levulinic acid yield were established by statistical modeling of experimental data. Operating under the best reaction conditions (at 191.2°C for 18.9 min in aqueous media containing 1.10% HCl), the levulinic acid yield accounted for 56.4% of the stoichiometric value.     

Manufacture of Microcrystalline Cellulose from Eucalyptus globulus Wood Using an Environmentally Friendly Biorefinery Method

In this work, hemiceluloses and lignin were solubilized by successive steps of autohydrolysis and delignification, and the resulting solids were processed to obtain microcrystalline cellulose. Eucalyptus globulus wood chips were treated with hot, compressed water under selected conditions to cause the hydrolytic breakdown of heteroxylan into substituted saccharides. The xylan-depleted solids were treated with acetic acid under optimized conditions to remove lignin, leaving a solid phase with high cellulose content. This latter was subjected to Totally Chlorine Free (TCF) bleaching to yield microcrystalline cellulose. These sequence autohydrolysis-organosolv delignification-TCF bleaching enabled the selective separation of hemicelluloses (which were mainly converted into soluble saccharides), lignin (as compounds soluble into acetic acid), and microcrystalline cellulose, according to an environmentally friendly biorefinery method.     

Selecting the Pre-Hydrolysis Conditions for Eucalyptus Wood in A Fractional Exploitation Biorefining Scheme

The operating conditions for the autohydrolysis of eucalyptus wood were optimized with a view to maximizing hemicellulose extraction while preserving the integrity of glucan. The influence of the operating conditions used in the soda–anthraquinone pulping of the solid phase resulting from the autohydrolysis process was examined. Autohydrolysis of the raw material at a liquid/solid ratio of 8 kg water/kg material at 180°C for 30 min was found to provide a commercially useful liquid phase containing most of the starting hemicellulose. The autohydrolysis treatment allowed the subsequent production of soda–anthraquinone cellulose pulp and paper with properties as good as or even better than those obtained without the pretreatment.     

Infrared Absorption Spectra of Cellulose Pulps of Palm Tree

Palm leaves are used for the production of different cellulose pulps; their properties are investigated, the resulting pulps were bleached by a multistage process, the effects of the addition of solvent during the pulping process on the chemical structure of the pulps are discussed. The strength properties of the paper which is produced from unbleached and bleached pulps increased with increasing cellulose percentage and decreasing lignin content in the pulp. Infrared absorption spectra were recorded for different unbleached and bleached pulp in the frequency range 200–4000 cm^-1 by using the alkali halide disk technique; the factors which affect the experimental technique were calibrated through these studies. The structural units within pulping yield (holocellulose, hemicellulose, cellulose, lignin, and ash) were interpreted within the pulp network structure by the infrared absorption spectra, where different samples of unbleached, bleached soda, and kraft pulps were also elucidated by IR spectra, after preheating at different temperatures and with using different ratios of organic solvents. The addition of organic solvents decreased or increased the crystallinity indices, depending on the type of solvent and the pulping temperature. It was also found that, at the same pulping temperature (155°C) and with the same percent of organic solvents in the pulping liquor, the asymmetry indices also the mean hydrogen bonding strength (A _OH/A_CH) of the unbleached soda pulps (organosolv or nonorganosolv pulping) were less than that of unbleached kraft pulps, except for the pulps obtained by pulping with dioxan at 155°C. The mean hydrogen bond strength of the bleached pulps decreased or increased, depending on the type solvent used and the pulping temperature.     

Structural Variation of Bamboo Lignin before and after Ethanol Organosolv Pretreatment

In order to make better use of lignocellulosic biomass for the production of renewable fuels and chemicals, it is necessary to disrupt its recalcitrant structure through pretreatment. Specifically, organosolv pretreatment is a feasible method. The main advantage of this method compared to other lignocellulosic pretreatment technologies is the extraction of high-quality lignin for the production of value-added products. In this study, bamboo was treated in a batch reactor with 70% ethanol at 180 °C for 2 h. Lignin fractions were isolated from the hydrolysate by centrifugation and then precipitated as ethanol organosolv lignin. Two types of milled wood lignins (MWLs) were isolated from the raw bamboo and the organosolv pretreated residue separately. After the pretreatment, a decrease of lignin (preferentially guaiacyl unit), hemicelluloses and less ordered cellulose was detected in the bamboo material. It was confirmed that the bamboo MWL is of HGS type (p-hydroxyphenyl (H), vanillin (G), syringaldehyde (S)) associated with a considerable amount of p-coumarate and ferulic esters of lignin. The ethanol organosolv treatment was shown to remove significant amounts of lignin and hemicelluloses without strongly affecting lignin primary structure and its lignin functional groups.     

Fractionnement de deux bois tropicaux (eucalyptus et wapa) par traitement thermomécanique en phase aqueuse. Partie II: Caractéristiques chimiques des résidus et considérations cinétiques sur la solubilisation des hémicelluloses

We have characterized the residual solids derived from the aqueous phase liquefaction of two tropical wood species. The liquefaction process comprises the following steps: preparation of an aqueous suspension of milled wood, preheating at 135°C, sudden decompression through an orifice (ΔP = 17.2 MPa), reaction at 80–230°C and rapid quenching. The residues have been analyzed by two methods: acid hydrolysis and elemental analysis. The quantification of the monosaccharides present in the residues allows us to follow the solubilization profiles of both hemicelluloses and cellulose. The elemental composition of the residues is related to the severity of the process and it becomes a solubilization index for the hemicelluloses and the lignin. The chromatographic analysis of the gaseous phase after liquefaction has resulted in the determination of CO₂ as the only gas produced up to 230°C. Kinetic first order models represent well the solubilization of the hemicelluloses and the CO₂ formation.     

BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. II. ANALYSIS BY NMR,ESI/MS,AND GPC

ABSTRACT

Residual and dissolved lignin from different phases of kraft delignification of Eucalyptus globulus wood were isolated and characterized by 1D and 2D ¹H NMR, ¹³C NMR, Electrospray Ionization Mass Spectrometry (ESI/MS), and gel permeation chromatography (GPC). During the temperature rise period, below 70°C, about 20% of the lignin was dissolved without significant structural changes. Above 70°C, the lignin suffered significant degradation/fragmentation in the cell wall prior to dissolution. The lignin ether-linked syringyl units were the most susceptible to alkaline degradation. Through the course of pulping, the residual lignin (RL) revealed a gradual increase of aliphatic moieties of unknown structure, as well as a decrease of native structures such as phenylcoumaran and pino-/syringaresinol lignin units. A significant decrease of the β-O-4 structures content in RL was detected only at the final cooking temperature. The lignin dissolved in the black liquor (BL) consisted of highly branched oligomers with rather low molecular weight (average mass 800–1000 u). A part of BL (about 30%) was chemically linked to carbohydrates and possessed a large molecular weight distribution (500–4000 u). BL showed a progressive decrease in β-O-4 and pino-/syringaresinol structures and formation of enol ether and stilbene structures. The GPC analyses showed a continuous decrease of the molecular weight of both the residual and dissolved lignins during the pulping process, particularly in the residual stage.     

Effect of several factors on peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis

BACKGROUND: Lignocellulose should undergo pretreatment to enhance its enzymatic digestibility before being saccharified. Peracetic acid (PAA) is a strong oxidant that can remove lignin under mild conditions. The sulfuric acid in the PAA solution also can cause degradation of hemicelluloses. The objective of the present work is to investigate the effect of several factors on peracetic acid pretreatment of sugarcane bagasse. RESULTS: It was found that PAA charge, liquid/solid (l/s) ratio, temperature, time, interactions between PAA charge and l/s ratio, temperature and time, all had a very significant effect on the enzymatic conversion ratio of cellulose. The relative optimum condition was obtained as follows: PAA charge 50%, l/s ratio 6:1, temperature 80 °C and time 2 h. More than 80% of the cellulose in bagasse treated under the above conditions was converted to glucose by cellulase of 20 FPU g^?1 cellulose. Compared with H₂SO₄ and NaOH pretreatments under the same mild conditions, PAA pretreatment was the most effective for enhancement of enzymatic digestibility. CONCLUSION: PAA pretreatment could greatly enhance the enzymatic digestibility of sugarcane bagasse by removing hemicelluloses and lignin, but removal of lignin was more helpful. This study can serve as a step to further optimization of PAA pretreatment and understanding the mechanism of enhancement of enzymatic digestibility. Copyright © 2007 Society of Chemical Industry     

Systematic Isolation and Utilization of Lignocellulosic Components from Sugarcane Bagasse

Lignocellulosic constituents as renewable feedstock can be utilized for various applications. A systematic procedure for separation of cellulose and lignin followed by hydrolysis of hemicelluloses was proposed in this study. Sugarcane bagasse was first subjected to alkaline hydrolysis to remove lignin and hemicelluloses. Then cellulose was separated from the alkali pretreatment residue and further purified. Meanwhile, the obtained pre-hydrolysis liquor (PHL) was acidified to precipitate lignin, and the filtrate was hydrolyzed with 1-methylimidazolium hydrogen sulfate ([Hmim]HSO₄) to prepare furfural. Response surface methodology (RSM) was employed to determine optimal conditions for isolation of cellulose. The sequential treatments resulted in a total release of over 77.3% of the original cellulose and 84.5% of the original lignin. In particular, 7.5% yield of furfural was obtained. The structures of the isolated cellulose and lignin were elucidated with Fourier transform infrared spectroscopy (FT-IR).     

枫香树材硫酸盐法蒸煮历程

研究了枫香树材硫酸盐法蒸煮过程中木素、戊聚糖和纸浆得率的变化。结果表明,枫香硫酸盐法蒸煮脱木素可分为以下三个阶段:第一阶段,升温到155℃,属于初始脱木素阶段,木素脱除率达到22.5%左右,戊聚糖溶出30.16%,得率为70.48%;第二阶段,从155℃开始到165℃保温60 min,属于大量脱木素阶段,木素脱除率达93.74%,戊聚糖溶出48.31%,得率为47.43%;第三阶段,从165℃保温60 min后到蒸煮末期,属于残余脱木素阶段,木素脱除率达到98%左右,戊聚糖溶出51.04%,得率为43.87%。     

木素化学研究与制浆技术的进展

本文综述了木素化学与制浆技术的研究进展。介绍了碱法制浆中添加蒽醌的作用、有机溶剂制浆、深度脱木素和无氯漂白，以及当代木素化学所面临的课题。评述了有关高得率浆的返色、未漂硫酸盐浆中的残余木素、漂白过程中有机氯化合物的形成及其毒性，以及无氯漂白等的研究发展近况．     

Bioethanol production from biomass: carbohydrate vs syngas fermentation

Environmental problems associated with the use of fossil fuels as well as their expected scarcity in the near future requires a search for new alternative fuels produced from renewable sources. Bioethanol is a biofuel that can be obtained from biomass and waste as feedstocks through fermentation. Two major routes allow conversion of the feedstocks to fermentable substrates, i.e. the hydrolytic route and the thermochemical route. In the hydrolytic route, the feedstock undergoes a pretreatment stage first, aimed at facilitating the subsequent hydrolytic treatment. Chemical, physical or biological pretreatments can be applied. Lignocellulosic feedstocks are mainly composed of cellulose, hemicellulose and lignin. The pretreatment attacks the lignin and hemicellulose polymers and makes cellulose more accessible in the next, hydrolytic, stage. The hydrolytic treatment uses enzymes to convert the cellulose polymer to simple, fermentable, sugars, mainly glucose. Simple sugars obtained from hemicellulose and cellulose are then fermented by yeasts to bioethanol. In the thermochemical alternative, the feedstock is gasified, yielding syngas – a mixture largely composed of CO, CO₂ and H₂ – which can be fermented anaerobically, usually by clostridia, to ethanol or other products. In both cases, downstream processes are then applied to recover and purify the biofuel. The different stages involved in both alternatives are described, and both processes are compared in terms of their main characteristics and development stage. © 2015 Society of Chemical Industry     

Fractionation of woodmeal by prehydrolysis and thermal organosolv. Process strategy,recovery of constituents,and solvent fractionation of lignins so produced

A prototype hardwood Populus deltoids has been fractionated in kg quantities into its primary constitutive polymers, namely, cellulose, hemicelluloses, and lignin, under optimal recovery conditions for each fraction. Our approach is targeted at processing sawdust or finally divided wood (d_p ≤ 0.5 mm) and involves a thermomechano-solvolytic treatment of medium consistency suspensions in two process development units operated sequentially. Firstly, the hemicellulose fraction is removed from the initial wood by a aqueous-steam pretreatment (auto-hydrolysis) at conditions where nearly 90% of the hemicelluloses are solubilized. Secondly, the treated wood (lignocellulose) is separated into cellulose and lignin rich fractions by subjecting it to an organosolvolytic treatment using ethylene glycol as solvent. An experimental unit which can be operated in semi-continuous or continuous modes is described and was employed for this step. The recovery of each fraction via appropriate mass balances is presented. Also, a comparative characterization of the lignins isolated via (a) the direct solvolysis route and (b) the sequential aqueous-steam pretreatment followed by solvolysis approach is made using solvent fractionation, molar mass distribution, and ¹³C NMR spectroscopy methods.     

Tetrahydrofurfuryl Alcohol (THFA) Pulping of Rice Straw

Abstract

A 80–95% solution of tetrahydrofurfuryl alcohol (THFA) added with 0.15–0.5% catalytic hydrochloric acid (HCl) was used to pulp rice straw. The pulping conditions applied for organosolv digestions of the straw at atmospheric pressure and 120°C cooking for 4 h. The characteristics of the digestion, chemical properties of the resulting pulp, and the handsheet physical properties were evaluated. As for the pulp yields, the method has high delignification specificity, at kappa number 20, the yield was ca. 60%, about 15–20% higher than the traditional alkaline pulping method. Furthermore, with increasing THFA concentrations, efficacies of delignification also increased. Increasing the catalyst dosage also caused an increase in delignification. Delignification rate of 120°C cooking are not so appreciable, but high yield were retained. If cooking temperatures were increased to 130 and 150°C, although even higher delignification rates were achievable, the yield decreased as well. During the cooking the dissolution of carbohydrate was low, at most 23%, consisting of mostly hemicelluloses, which was as high as 78% of the dissolved carbohydrates. The optimal conditions of the THFA/HCl cooking applied 95% THFA, 0.50% HCl, temperature of 120°C, and cooking time of 240 min. Residue lignin in the resulting pulp was low, and can be bleached to high brightness easily with a conventional bleaching sequence. If, however, energy and operation efficiency was a primary consideration, then a procedural heating scheme could be employed. The physical properties of the THFA pulp handsheets were inferior to those of the kraft pulp. The main reason was the damage to cellulose sustained during the acidic cooking condition.     

Formation and Reaction of Coniferyl Alcohol During Alkaline Pulping

The formation and subsequent disappearance of coniferyl alcohol during kraft and soda-AQ (anthraquinone) pulping of western hemlock wood meal have been studied under isothermal condition. At 140°C, the amount of coniferyl alcohol generated increases to a sharp maximum (0.4% of total lignin in kraft and 1.9% in soda-AQ pulping) and then declines rapidly to low values. It was found that the disappearance of coniferyl alcohol was mainly due to condensation with other components of dissolved lignin. Nearly identical activation energies, 125 kJ mole^?1 for kraft and 128 kJ mole^?1 for soda-AQ pulping, were derived from the initial rates of coniferyl alcohol formation, conforming closely with the value 121 kJ mole^?1 for the cleavage of phenolic β-ether model compounds in the kraft process.     

TCF BLEACHED PULPS FROM MISCANTHUS SINENSIS BY THE IMPREGNATION RAPID STEAM PULPING (IRSP) PROCESS

ABSTRACT

The production of bleached cellulose pulps from elephant grass (Miscanthus sinensis) via a two-stage soda pulping process and a TCF bleaching sequence is evaluated in this work. The impregnation rapid steam pulping process (IRSP) involves impregnating of the lignocellulosic material with the pulping liquor, withdrawing the excess liquor and rapidly steaming the impregnated material at 180–200°C for a short time. In this paper the process variables and their effect on the kappa number, yield and viscosity of the unbleached pulps are discussed. Bleaching by an ozone-based TCF sequence was tested, and the papermaking properties of the bleached pulp were determined. A kappa number of 19 was obtained by impregnating at an alkali charge of 30 + 0.1% anthraquinone carboxylic acid (AQCA) and pulping at 180°C for only 15 min. Kappa was reduced to 16 by extending pulping time to 26 min. The alkali consumption during impregnation and pulping was 10.2 g NaOH/100 g of dry Miscanthus. Screened pulp yield, viscosity and brightness for this pulp were 54.6%, 913 mL/g and 37.3%, respectively. After bleaching, the pulp had an ISO brightness of 87.4% and a viscosity of 700 mL/g. Refining in a PFI mill provided optimal strength properties of the bleached pulp at 4500 revolutions (71°SR): breaking length 7.2 km, tensile index 72 N m/g, and burst index 4.3 kN/g. Tear index was 7.9 mN m²/g at this degree of refining.     

Fractionnement de deux bois tropicaux (eucalyptus et wapa) par traitement thermomécanique en phase aqueuse. Partie I: Conversion et profils de solubilisation

The conversion and solubilization profiles of two species of tropical woods have been studied via an aqueous phase thermo-mechanical treatment. An aqueous wood suspension having a consistency of 8% solids is preheated (digestion at 135°C) and caused to flow through a capillary at speeds between 50 and 115 m/s. At the exit of the capillary, a flash decompression facilitates disaggregation of the hemicelluloses–lignin–cellulose complex. The separation of hemicelluloses and lignin has been studied as a function of the treatment severity (150–230°C). The results presented lead to the conclusion that a selective and sequential fractionation of the compound lamella lignin and the hemicelluloses is possible for the tropical species studied. The optimum operational conditions are discussed based on the experimental observations.     

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.     

NMR analysis of the transformation of wood constituents by torrefaction

The injection of biomass in a pressurised entrained flow reactor is challenging. Biomass preparation by torrefaction before gasification could be a suitable option to improve it. Transformation of the material induced by this treatment lead to interesting features: increased brittleness, improved fluidisation properties of the powder, hydrophobicity, higher energy content. The major biomass constituents, cellulose, hemicelluloses and lignin are variously affected by torrefaction, depending on their respective reactivity. The objective of this work is to investigate the transformation of the biomass constitutive polymers induced by this thermal treatment. For that purpose, both solid-state NMR and EPR investigations have been performed on wood samples (beech) torrefied at different temperatures ranging from 200 °C to 300 °C. The results of these investigations have been compared with data obtained on untreated wood. These characterizations have brought to light different transformations of the polymers: de-acetylation of hemicelluloses, demethoxylation of lignin, changes in the cellulose structure. Furthermore, the temperature at which depolymerisation of the different components begins to occur has been identified.