Anna Sundberg

Polysaccharides in some industrially important hardwood species

The amount and composition of sugar units comprising polysaccharides in sapwood and heartwood, or stemwood, of 11 industrially important pulpwood species were analysed. The polysaccharide content was between 60 and 80% (w/w) for all species, with cellulose as the predominant polysaccharide type and glucuronoxylans as the main non-cellulosic polysaccharides. The second most abundant non-cellulosic polysaccharides were either pectins, i.e. polygalacturonic acids, or glucomannans. The amount of acidic sugar units were 15–23% of the total amount of non-cellulosic sugar units in all samples, with the Acacia species in the high end. The amount and composition of water-soluble carbohydrates from ground wood samples were also analysed, since these are important in mechanical and chemimechanical pulping, and as a possible source of bioactive polymers. Sapwood released more carbohydrates than heartwood for most species. It is to be noted that the relative amount of dissolved acidic sugar units was larger from the heartwood than from the sapwood for all species. Probably due to the mild treatment conditions, the main dissolved polysaccharides were xylans only for a few samples, while easily soluble galactans, arabinogalactans, or mannans dominated in most species. Pectins dominated in heartwood of Populus grandidentata. Generally, pectins and acidic xylans were the main acidic polysaccharides.

Knots in trees - A new rich source of lignans

Recent research in our group has revealed that knots, i.e. the branch bases inside tree stems, commonly contain 5–10% (w/w) of lignans. Norway spruce (Picea abies) knots contain as much as 6–24% of lignans, with 7-hydroxymatairesinol (HMR) as the predominant (70–85%) lignan. Some other spruce species also contain HMR as the main lignan, but some spruce species have also other dominating lignans. Most fir (Abies) species contain secoisolariciresinol and lariciresinol as the main lignans. Lignans occur also in knots of pines (Pinus spp.), although in lower amounts than in spruces and firs. Scots pine (Pinus silvestris) knots were found to contain 0.4–3% of lignans with nortrachelogenin as the main lignan. Lignans have been identified also in knots of some hardwoods, although flavonoids are more abundant in hardwoods. Knots are detrimental in the manufacture of pulp and paper and should preferably be removed before pulping. This is possible using a recently developed industrially applicable process called ChipSep. Recent research has also established novel synthetic routes to several lignans, such as matairesinol, secoisolariciresinol, lariciresinol and cyclolariciresinol, starting from hydroxymatairesinol by applying fairly straight-forward chemical transformations. We conclude that wood knots in certain spruce and fir species constitute the richest known source of lignans in nature. The lignans occur in knots in free form and are easily extracted by aqueous ethanol, or even by water. Not only HMR, but also other potentially valuable lignans, could be produced in a scale of hundreds of tons per year by extraction of knots separated from wood chips at pulp and paper mills.

Distribution of Anionic Groups in TMP Suspensions

Abstract The distribution of anionic groups in fibres, fines, the colloidal fraction, and the dissolved fraction of thermomechanical pulp (TMP) suspensions was determined. The influence of extraction, alkaline treatment, and peroxide bleaching of spruce TMP were also studied. Spruce TMP was extracted with hexane, treated with alkali, or bleached with peroxide. Suspensions were made at pH 5.5 or 8, and fractionated into long fibres, large fines, small fines, a colloidal fraction, and a dissolved fraction. The surface and total charge of the fractions were determined separately by polyelectrolyte titration. To determine the origin of the charges, the contents of fatty acids, resin acids, and acidic units in polysaccharides in the different fractions were determined by gas chromatography. Extraction of TMP with hexane prior to fractionation increased the measured total and surface charge of the fibres. The removal of wood resin probably uncovered some anionic groups on the fibre surface, or improved the penetration of the polymers into the pores of the fibres. The total charge, determined with polybrene titration, of the fines and the colloidal fraction was lower when the resin had been removed, while the surface charge, determined with poly-DADMAC, was not greatly affected. Alkaline treatment of the TMP increased both the total charge and the surface charge of the fibres and fines, mainly because of demethylation of pectins. Alkaline treatment also increased the total and surface charge of the dissolved substances, due to the release of pectic acids into the water phase. Alkaline peroxide bleaching further increased the total and surface charge of fibres and dissolved substances, most likely due to oxidation of lignin. The total charge and the surface charge of the colloidal substances, consisting mainly of wood resin, were only slightly affected by alkaline treatment and peroxide bleaching. The anionic charge in TMP suspensions originated mainly from free uronic acids in the xylans, arabinogalactans, and pectic acids. The contribution from the fatty and resin acids was substantial only for the colloidal fraction.

Hydrophobication and characterisation of O-acetyl-galactoglucomannan for papermaking and barrier applications

Norway spruce O-acetyl-galactoglucomannans (GGM) are water-soluble hemicelluloses that have potential to be produced in large scale as a side product of the mechanical pulping industry or by hot-water extraction of wood. Chemical modification is often needed to tailor such water-soluble polysaccharides into industrially valuable compounds. In this work, treatment of GGM with butyric and benzoic anhydride in pyridine/dimethylformamide rendered GGM derivatives, which were hydrophobic and partially soluble in organic solvents. The degree of substitution can be adjusted by varying the quantity of the reagent and reaction temperature. The dn/dc value for the benzoyl ester of GGM was determined in 0.05 M LiBr DMSO in order to obtain accurate molar mass analysis with SEC-MALLS-RI. Novel substances with adjusted hydrophobicity can thus be prepared on one step synthesis from natural hemicelluloses, which then showed a slight increase in the molar mass upon esterification.

Phase Distribution of Resin and Fatty Acids in Colloidal Wood Pitch Emulsions at Different pH-Levels

The distribution of resin and fatty acids (RFAs) between the water phase and the lipophilic phase in colloidal pitch emulsions was determined as a function of pH. Model pitch emulsions were prepared and agitated at different pH, temperature, and NaCl concentration. After filtration, the concentration of dissolved RFAs in the water phase was determined. The experimental data were used for calculation of pKlw, that is, the pH at which 50% of the acids are dissolved in the water phase. At pH 3, all of the RFAs were associated with the colloidal droplets. The resin acids were dissolved at lower pH than the fatty acids. Among the resin acids, dehydroabietic acid had the lowest pKlw. The pKlw of fatty acids depended greatly on the chain length and degree of unsaturation. Fatty acids with more than 20 carbon atoms had a low water solubility even above pH 10. Increasing the NaCl concentration increased the pKlw. The kinetics of the phase distribution was very rapid.

Cationised O-acetyl galactoglucomannans: Synthesis and characterisation

Water-soluble O-acetyl-galactoglucomannans (GGMs) can be obtained from Norway spruce by hot-water-extraction of the wood or as a side product by ultrafiltration of mechanical pulping waters. Cationic and amphiphilic polysaccharides and their derivatives are of interest for a number of applications and thus quaternary nitrogen moieties with cationic charge were grafted onto GGMs in the heterogeneous reaction to render a cationic polyelectrolyte. The degree of substitution was measured by elemental analysis of nitrogen, by quantitative (13)C NMR and interestingly also by polyelectrolyte titration and the results were congruent. NMR, matrix-assisted laser desorption/ionisation mass spectroscopy (MALDI-TOF-MS), and FT-IR analysis were used to characterise the product. THF or DMSO with water enhanced the reaction efficiency and decreased M(w) reduction in comparison to plain water as a reaction media. Cationised GGM was also successfully acetylated. The cationic derivatives of hemicelluloses can potentially be utilised as polyelectrolyte layers in packaging and pharmaceutical applications.

CHARGED GROUPS IN WOOD AND MECHANICAL PULPS

ABSTRACT Analysis by acid methanolysis and gas chromatography revealed that galacturonic acid, which is the main sugar unit in pectin, was the most abundant uronic acid in Nordic spruce, pine, birch and aspen wood, as well as in mechanical pulps. However, since most of the galacturonic acids are methylesterified in native wood, the 4-O-methyl glucuronic acid in xylan is the main charged group in wood and in mechanical pulps. Mechanical pulp fines were found to contain much more galacturonic acid, rhamnose, arabinose and galactose, and slightly more xylose and methylglucuronic acid, than the long fibre fractions. Alkaline treatment of mechanical pulp more than doubled the fibre charge, and alkaline peroxide bleaching produced still more new acid groups. Charged groups were formed in the fibres with the same kinetics as the release of methanol and acetic acid. It was concluded that the new acid groups originate mainly from demethylation of pectin, and in case of peroxide bleaching also from oxidation of lignin.

Structural, histochemical and chemical characterization of normal, tension and opposite wood of Subabul (Leucaena leucocephala (lam.) De wit.)

Structure, histochemistry and chemical composition of tension (TW), opposite (OW) and normal wood (NW) of Leucaena leucocephala have been studied using histological, histochemical and biochemical methods. TW vessels are longer and have a larger diameter than NW vessels, and the rays are shorter and thinner. The G-layer replaced S3 and parts of S2 wall layers in TW fibres. TW further contained less lignin that also had a lower syringyl-to-guaiacyl ratio. The lignin was also more condensed. The content of α-cellulose was high in TW. TW contains hemicelluloses and pectins composed of more galactose, and less xylose, mannose, 4-O-methylglucuronic acid and galacturonic acid compared to that of OW. This study suggests that in the TW of Leucaena, the amount and composition of lignin, hemicelluloses and pectins differ considerably from that in OW and NW.

Influence of Pitch Composition and Wood Substances on the Phase Distribution of Resin and Fatty Acids at Different pH Levels

Pitch emulsions were prepared to mimic the colloidal wood resin system in paper mill process waters. The phase distribution of resin and fatty acids (RFAs) between the colloidal lipophilic droplets (l) and the water phase (w) were determined as pKlw values. The effect of triglyceride to RFA ratio on pKlw values was studied, to determine if seasonal variations in wood extractives influence their phase distribution. The effect of water-soluble hemicelluloses on pKlw values was also determined. The pKlw values of the RFAs were lower in emulsions with a low triglyceride to RFA ratio. Addition of water-soluble galactoglucomannans also lowered the pKlw values of the RFAs.

Selective purification of bleached spruce TMP process water by induced air flotation (IAF)

Abstract The environmentally benign closure of water systems in paper mills leads to the problem of accumulation of dissolved and colloidal wood substances (DCS) in process water. Notably, pitch affects the pulp and paper production negatively and increases the demand for additional treatment of the process water. In the present article, the purification of thermomechanical pulping process water from the alkaline peroxide bleaching stage has been investigated, with the induced air flotation (IAF) in focus. The following parameters were considered concerning the IAF efficiency to remove detrimental substances: concentration of cationic foaming agent, pH value, calcium concentration, and temperature. The amounts and characteristics of residual DCS were determined by gas chromatography and turbidity measurements. Residual concentrations of the foaming agent dodecyltrimetylammonium chloride were determined by electrospray ionization mass spectrometry. Up to 90% of pitch was removed, whereas hemicelluloses, which are important in preventing pitch problems, remained in the waters. Up to 70% of the pectic acids accounted for the high cationic demand of the process waters were removed by optimization of the IAF parameters. The presented separation process gives new opportunities to a selective purification of the process waters.