Birch Wood Lignin Research Articles

Copper-catalyzed C–C bond cleavage coupling with C[tbnd]N bond formation toward mild synthesis of lignin-based benzonitriles

N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals. The vast majority of developed strategies employ organic amines as nitrogen source, and considerable methods rely on excessive use of strong base, which suffers severe environmental issues. Herein, benzonitrile derivatives are synthesized from oxidized lignin β-O-4 model compounds in the presence of solid nitrogen source (NH4)2CO3 under mild, base-free conditions over commercially available copper catalyst. Mechanism studies suggest the transformation undergoes a one-pot, highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of CN bond. Of which, Cu(OAc)2 catalyzes the transfer of hydrogen from Cβ (Cβ-H) to Cα, leading to the cleavage of Cα-Cβ bonds to offer benzaldehyde derivative, this intermediate then reacts in-situ with (NH4)2CO3 to afford the targeted aromatic nitrile product. Tetrabutylammonium iodide (TBAI), acting as a promoter, plays a key role in breaking the Cα-Cβ bonds to form the intermediate benzaldehyde derivative. With this protocol, the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated. This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.

Synthesis of 2,6-Dimethoxy-p-aminophenol from Hardwood Lignin.

Although the multiple functional groups in biomass offer notable chances for producing high-value chemicals, most of the current studies focused on the (deep) defunctionalization of biomass and its derivates. Herein, we present a catalytic approach to valorize birch wood lignin with maintaining the methoxy and hydroxy groups in the final product (i. e., 2,6-dimethoxy-p-aminophenol), which has applications in different sectors such as pharmaceuticals. The proved approach involves four steps with a high yield (19.8 wt % on the basis of used lignin) to 2,6-dimethoxy-p-aminophenol. The native lignin in birch wood was first converted using alkaline aerobic oxidation in the presence of copper ions toward high-yield syringaldehyde, which was then selectively oxidized toward 2,6-dimethoxy-1,4-benzoquinone using H2 O2 and V2 O5 . Oximation of 2,6-dimethoxy-1,4-benzoquinone can selectively form 2,6-dimethoxy-1,4-benzoquinone-4-oxime, which can be quantitatively hydrogenated toward 2,6-dimethoxy-p-aminophenol. This work highlights the unique potential of biomass and its derivates for the sustainable production of high-value products with exploring the value of inherent functional groups.

Effect of metal triflates on the microwave-assisted catalytic hydrogenolysis of birch wood lignin to monophenolic compounds

The lignin-first biorefinery strategy could produce bio-based phenols from the extraction and depolymerization of native lignin in lignocellulosic biomass. Herein, we report an effective Lewis acid-promoted delignification and production of monophenolic compounds in birch sawdust assisted by microwave heating without external hydrogen for the first time. The screening of different metal triflates revealed that Fe(OTf)3 was best for the delignification and depolymerization of birch sawdust. Without the addition of a Lewis acid, the yield of monophenolic compounds was 10.5 wt% (based on the lignin content in birch sawdust), while it increased significantly to 32.9 wt% with the addition of Fe(OTf)3 (0.0276 g) under the identical conditions (190 °C, 1 h), which demonstrated the catalytic COC bond scission promoted by Fe(OTf)3. Simultaneously, the delignification degree also rose sharply from 32.6 wt% to 47.5 wt%. This work demonstrated the efficient Fe(OTf)3-induced delignification and depolymerization of lignin in birch sawdust to obtain a high yield of monophenolic compounds without external hydrogen assisted by microwave heating, representing a novel advance in the “lignin-first” biorefinery field.

The natural catalytic function of CuGE glucuronoyl esterase in hydrolysis of genuine lignin\u2013carbohydrate complexes from birch

BackgroundGlucuronoyl esterases belong to carbohydrate esterase family 15 and catalyze de-esterification. Their natural function is presumed to be cleavage of ester linkages in lignin–carbohydrate complexes particularly those linking lignin and glucuronoyl residues in xylans in hardwood.ResultsHere, we show for the first time a detailed product profile of aldouronic acids released from birchwood lignin by a glucuronoyl esterase from the white-rot fungus Cerrena unicolor (CuGE). CuGE releases substrate for GH10 endo-xylanase which results in significantly increased product release compared to the action of endo-xylanase alone. CuGE also releases neutral xylo-oligosaccharides that can be ascribed to the enzymes feruloyl esterase side activity as demonstrated by release of ferulic acid from insoluble wheat arabinoxylan.ConclusionThe data verify the enzyme’s unique ability to catalyze removal of all glucuronoxylan associated with lignin and we propose that this is a direct result of enzymatic cleavage of the ester bonds connecting glucuronoxylan to lignin via 4-O-methyl glucuronoyl-ester linkages. This function appears important for the fungal organism’s ability to effectively utilize all available carbohydrates in lignocellulosic substrates. In bioprocess perspectives, this enzyme is a clear candidate for polishing lignin for residual carbohydrates to achieve pure, native lignin fractions after minimal pretreatment.

Tungsten Carbide: A Remarkably Efficient Catalyst for the Selective Cleavage of Lignin C-O Bonds.

A remarkably effective method for the chemoselective cleavage of the C-O bonds of typical β-O-4 model compounds and the deconstruction of lignin feedstock was developed by using tungsten carbide as the catalyst. High yields of C-O cleavage products (up to 96.8 %) from model compounds and liquid oils (up to 70.7 %) from lignin feedstock were obtained under low hydrogen pressure (0.69 MPa) in methanol. The conversion efficiency was determined to a large extent by solvent effects and was also affected by both the electronic and steric effects of the lignin model compounds. In situ W2 C/activated carbon (AC)-catalyzed hydrogen transfer from methanol to the substrate was proposed to be responsible for the high performance in methanol solvent. The conversion of 2-(2-methoxyphenoxy)-1-phenylethanol showed that the catalyst could be reused five times without a significant loss in activity for C-O bond cleavage, whereas the selectivity to value-added styrene increased markedly owing to partial oxidation of the W2 C phase according to X-ray diffraction, Raman spectroscopy, and transmission electron microscopy characterization. 2 D-HSQC-NMR spectroscopy analysis showed that W2 C/AC exhibited high activity not only for β-O-4 cleavage but also for the deconstruction of more resistant α-O-4 and β-β linkages, so that a high yield of liquid oil was obtained from lignin. Corn stalk lignin was more liable to be depolymerized than birch lignin owing to its loosened structure (scanning electron microscopy results), larger surface area (BET results), and lower molecular weight (gel-permeation chromatography results), whereas its liquid oil composition was more complicated than that of birch wood lignin in that the former lignin contained more p-hydroxyphenyl units and the former contained noncanonical units.

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process

Valorization of native birch wood lignin into monomeric phenols over nickel-based catalysts has been studied. High chemoselectivity to aromatic products was achieved by using Ni-based catalysts and common alcohols as solvents. The results show that lignin can be selectively cleaved into propylguaiacol and propylsyringol with total selectivity >90% at a lignin conversion of about 50%. Alcohols, such as methanol, ethanol and ethylene glycol, are suitable solvents for lignin conversion. Analyses with MALDI-TOF and NMR show that birch lignin is first fragmented into smaller lignin species consisting of several benzene rings with a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction. The second step involves the hydrogenolysis of the fragments into phenols. The presence of gaseous H2 has no effect on lignin conversion, indicating that alcohols provide active hydrogen species, which is further confirmed by isotopic tracing experiments. Catalysts are recycled by magnetic separation and can be reused four times without losing activity. The mechanistic insights from this work could be helpful in understanding native lignin conversion and the formation of monomeric phenolics via reductive depolymerization.

Effects of hot water extraction in a batch reactor on the delignification of birch wood

The amount of residual lignin in birch wood after a hot water extraction in a batch reactor was investigated as a function of extraction temperature and time. A kinetic model fitting the experimental data was then developed to explain delignification of wood during a hot water treatment. Results showed that delignification kinetics involves simultaneous degradation and condensation reactions, with degradation of lignin being much faster than its condensation. Native lignin in wood was successfully modeled as the sum of two fractions with different degradation rates. The rates of degradation and condensation increased along with increasing extraction temperature. The proportion of acid-soluble lignin to acid-insoluble (Klason) lignin in the wood residue decreased with increasing extraction temperature and time, probably due to chemical and structural changes in the lignin during the hot water treatment. Condensed lignin was predominantly determined as Klason lignin. On the other hand, the amount of soluble lignin in the extraction liquor increased slightly with temperature, but remained mostly constant after any extraction time. An insoluble fraction in the liquor that originated from precipitated lignin fragments is believed to contain traces of degradation products from carbohydrates or other degradation compounds.

Pre-treatment of biomass with phosphoric acid prior to fast pyrolysis: A promising method for obtaining 1,6-anhydrosaccharides in high yields

Biomass was pre-treated with phosphoric acid and dried prior to analytical pyrolysis. The influence of pre-treatment parameters—i.e. concentration of phosphoric acid, its uptake by biomass, and drying temperature—upon the pyrolysis process of various cellulose containing raw materials has been studied. The concentration of the impregnation solution should be chosen according to the sorption capacity of the cellulosic feedstock. By varying the concentration of phosphoric acid, the pyrolysis of microcrystalline cellulose Thermocell™ may be directed toward elevated production of levoglucosan (40%) and levoglucosenone (34%). The protective role of lignin in birch wood towards the cellulose moiety is discussed in connection with radical scavenging properties of lignin. Birch wood treated with phosphoric acid solutions (having concentrations less than 2%) yields approx. 15% levoglucosan. At higher concentrations, a decline of the radical scavenging activity of lignin occurs, which increments the role of dehydration reactions, and, as a consequence, the formation of more levoglucosenone (17%).

Kinetics of the bulk and residual delignification in kraft pulping of birch and factors affectingthe amount of residual phase lignin

The amount of lignin which needs to be removed according to the slow residual delignification phase in kraft pulping, i e residual phase lignin, has been studied as a function of the process conditions. The variebles studied were the concentrations of hydroxide ions, hydrogensulfide ions, sodium ions (ionic strength) and temperature. In addition, the amounts of residual phase ligning in the pulping of different lignocellulosic material were compared. Different additives can be applied to the kraft cook to improve the selectivity. Polysulfide sulfur is one of them and the effectt of polysulfide ions on the amount of residual phase lignin in kraft pulping was also investigated. It is shown, that the amounts of residual phase lignin in constant composition cooks (highliquor-to-wood ratio) of softwood (spruce), hardwood (birch) andgrass (wheat straw) are affected by the same factors in theinvestigated range. The amount of residual phase lignin isstrongly reduced by higher hydroxide ion concentration during the kraft cook and is to some extent decreased by higherhydrogensulfide ion concentration and lower sodium ionconcentration. These effects were not, however, found to bepurely additive for spruce wood, instead interactions occurred.In order to decrease the amount of residual phase lignin, it isessential to have a high concentration of hydrogensulfide ionswhen cooking with a low hydroxide ion concentration. The temperature has no effect on the amount of residual phase ligninin the range investigated. It is also shown that the lignin reacting according to theslow delignification phase is not a homogeneous lignin sincealteration of the conditions in the cook can make part of itreact as bulk phase lignin. This indicates that most of theresidual phase lignin is determined by the prevailing conditions,which determine how much of the native lignin reacts according tothe bulk and how much according to the residual delignificationmechanism. Pulping experiments carried out under the same conditions onwheat straw, birch wood and spruce wood also showed that theamount of residual phase lignin in wheat straw is only 30% of theamount of residual phase lignin in spruce wood, and that the amount of residual phase lignin in birch wood, is5 0% of the amount of residual phase lignin in sprucewood. The amount of residual phase lignin was affected by apolysulfide treatment. The amount of residual phase lignin was lowered by 30% for spruce wood and 10% for birch wood with apolysulfide treatment, compared with cooks without polysulfide. An explanation for this may be the finding that polysulfide can introduce a carboxylic acid function into the lignin, which will increase its water solubility, and reduce the need for fragmentation. An additional explanation may be the ability of polysulfides to degrade enol ether structures, which are normally more or less stable during kraft pulping.

The effect of polysulfide pretreatment when kraft pulping to very low kappa numbers

The amount of lignin which needs to be removed according to the slow residual delignification phase in kraft pulping, i e residual phase lignin, has been studied as a function of the process conditions. The variebles studied were the concentrations of hydroxide ions, hydrogensulfide ions, sodium ions (ionic strength) and temperature. In addition, the amounts of residual phase ligning in the pulping of different lignocellulosic material were compared. Different additives can be applied to the kraft cook to improve the selectivity. Polysulfide sulfur is one of them and the effectt of polysulfide ions on the amount of residual phase lignin in kraft pulping was also investigated. It is shown, that the amounts of residual phase lignin in constant composition cooks (highliquor-to-wood ratio) of softwood (spruce), hardwood (birch) andgrass (wheat straw) are affected by the same factors in theinvestigated range. The amount of residual phase lignin isstrongly reduced by higher hydroxide ion concentration during the kraft cook and is to some extent decreased by higherhydrogensulfide ion concentration and lower sodium ionconcentration. These effects were not, however, found to bepurely additive for spruce wood, instead interactions occurred.In order to decrease the amount of residual phase lignin, it isessential to have a high concentration of hydrogensulfide ionswhen cooking with a low hydroxide ion concentration. The temperature has no effect on the amount of residual phase ligninin the range investigated. It is also shown that the lignin reacting according to theslow delignification phase is not a homogeneous lignin sincealteration of the conditions in the cook can make part of itreact as bulk phase lignin. This indicates that most of theresidual phase lignin is determined by the prevailing conditions,which determine how much of the native lignin reacts according tothe bulk and how much according to the residual delignificationmechanism. Pulping experiments carried out under the same conditions onwheat straw, birch wood and spruce wood also showed that theamount of residual phase lignin in wheat straw is only 30% of theamount of residual phase lignin in spruce wood, and that the amount of residual phase lignin in birch wood, is5 0% of the amount of residual phase lignin in sprucewood. The amount of residual phase lignin was affected by apolysulfide treatment. The amount of residual phase lignin was lowered by 30% for spruce wood and 10% for birch wood with apolysulfide treatment, compared with cooks without polysulfide. An explanation for this may be the finding that polysulfide can introduce a carboxylic acid function into the lignin, which will increase its water solubility, and reduce the need for fragmentation. An additional explanation may be the ability of polysulfides to degrade enol ether structures, which are normally more or less stable during kraft pulping.

Thermal decomposition of inorganic polysulfides at kraft cooking conditions

The amount of lignin which needs to be removed according to the slow residual delignification phase in kraft pulping, i e residual phase lignin, has been studied as a function of the process conditions. The variebles studied were the concentrations of hydroxide ions, hydrogensulfide ions, sodium ions (ionic strength) and temperature. In addition, the amounts of residual phase ligning in the pulping of different lignocellulosic material were compared. Different additives can be applied to the kraft cook to improve the selectivity. Polysulfide sulfur is one of them and the effectt of polysulfide ions on the amount of residual phase lignin in kraft pulping was also investigated. It is shown, that the amounts of residual phase lignin in constant composition cooks (highliquor-to-wood ratio) of softwood (spruce), hardwood (birch) andgrass (wheat straw) are affected by the same factors in theinvestigated range. The amount of residual phase lignin isstrongly reduced by higher hydroxide ion concentration during the kraft cook and is to some extent decreased by higherhydrogensulfide ion concentration and lower sodium ionconcentration. These effects were not, however, found to bepurely additive for spruce wood, instead interactions occurred.In order to decrease the amount of residual phase lignin, it isessential to have a high concentration of hydrogensulfide ionswhen cooking with a low hydroxide ion concentration. The temperature has no effect on the amount of residual phase ligninin the range investigated. It is also shown that the lignin reacting according to theslow delignification phase is not a homogeneous lignin sincealteration of the conditions in the cook can make part of itreact as bulk phase lignin. This indicates that most of theresidual phase lignin is determined by the prevailing conditions,which determine how much of the native lignin reacts according tothe bulk and how much according to the residual delignificationmechanism. Pulping experiments carried out under the same conditions onwheat straw, birch wood and spruce wood also showed that theamount of residual phase lignin in wheat straw is only 30% of theamount of residual phase lignin in spruce wood, and that the amount of residual phase lignin in birch wood, is5 0% of the amount of residual phase lignin in sprucewood. The amount of residual phase lignin was affected by apolysulfide treatment. The amount of residual phase lignin was lowered by 30% for spruce wood and 10% for birch wood with apolysulfide treatment, compared with cooks without polysulfide. An explanation for this may be the finding that polysulfide can introduce a carboxylic acid function into the lignin, which will increase its water solubility, and reduce the need for fragmentation. An additional explanation may be the ability of polysulfides to degrade enol ether structures, which are normally more or less stable during kraft pulping.

The Distribution of Phenolic Hydroxyl Groups in Hardwood Lignins

Abstract Periodate oxidation, because of its high selectivity in the degradation of free-phenolic units, has been used along with the combined phenyl nucleus exchange and nitrobenzene oxidation techniques to estimate the distribution of phenolic hydroxyl groups in hardwood lignins. Analyses of the aspen and white birch wood lignin in situ indicate that the percentage of uncon-densed structures having a phenolic hydroxyl group was considerably higher for guaiacyl (∼20%) than for syringyl (−5%) units. Thus, the total phenolic hydroxyl groups of hardwood lignins are largely associated with the guaiacyl propane units.

Analysis of birch wood lignin by oxidative degradation

The lignin in birch wood has been subjected to analysis by oxidative degradation after milling of wood samples in a Wiley mill and in a rotatory ball mill. For comparison milled wood lignin from birch has also been analysed. It was found that the type of milling affects both the total yield of degradation acids and their relative frequency of occurrence. These findings are interpreted as being due to a cleavage of aryl ether linkages during the milling procedure.

Decomposition of14C-Labeled Maple and Spruce Lignin by Marine Fungi

Fungi occur on driftwood, intertidal wood, manila rope, and other lignocellulosic substrates in marine and estuarine environments (Johnson and Sparrow, 1961; Hughes, 1975; Kohlmeyer and Kohlmeyer, 1979). Several Ascomycetes and Deuteromycetes cause soft rots of wood submerged in seawater (Barghoorn and Linder, 1944; Henningsson, 1976). The marine basidiomycete Nia vibrissa Moore & Meyers causes a white rot (Leightley and Eaton, 1979). Relatively few fungi can decompose lignin, an extremely complex aromatic polymer (Crawford and Crawford, 1980; Crawford, 1981). Fukuzumi et al. (1975) demonstrated that the marine hyphomycete Dendryphiella salina (Sutherland) Pugh & Nicot could degrade sodium lignosulfonate, an industrially modified lignin. Henningsson (1976), using sulfuric acid hydrolysis to measure lignin content, found a strain of Zalerion maritimum (Linder) Anastasiou that degraded 12% of the lignin in birch wood in six months. Methods involving the use of 14C-labeled lignocellulosic substrates have made it possible to determine the amounts of lignin degraded by microorganisms to CO2 and water-soluble products (Crawford and Crawford, 1976). Using [lignin'4C]-lignocelluloses prepared from Norway maple and blue spruce as substrates, we measured the degradation of hardwood and softwood lignin by pure cultures of 12 marine and estuarine fungi. The fungi tested were Asteromyces cruciatus Moreau & Moreau ex Hennebert (F-156), Ceriosporopsis halima Linder (R-592), Corollospora maritima Werdermann (R-19), Dendryphiella salina (DS-1), Diplodia oraemaris Linder (F-162), Halosphaeria mediosetigera Cribb & Cribb (R-575), Heleococcum japonense Tubaki (R-692), Humicola alopallonella Meyers & Moore (F-164), Monodictys pelagica (Johnson) Jones (F-80), Nia vibrissa (RDB-8), Papulaspora halima Anastasiou (F-167), and Zalerion maritimum (R-6). Twigs of Norway maple (Acer platanoides L.) and blue spruce (Picea pungens Engelm.) were incubated with a solution of L-[U-14C]-phenylalanine to label the lignin (Crawford and Crawford, 1976). [Lignin-l4C]-lignocelluloses were prepared from the twigs by grinding and extracting the phloem layer (Crawford and Crawford, 1976). Specific activities of the maple and spruce lignocelluloses were 539 and 902 dpm mg-l, respectively. Triplicate culture tubes containing 50 mg of labeled lignocellulose each were autoclaved and 15 ml of a sterile liquid medium [oven-dried Rila Marine Salts (Rila Products, Teaneck, New Jersey) 20 g, yeast

Topochemistry of the fungal degradation of lignin in birch wood as related to the distribution of guaiacyl and syringyl lignins

Samples of non-decayed birch wood and samples decayed to weight losses of 21, 44, and 67% by Coriolus versicolor were subjected to acidolysis (4h reflux in dioxane-water, 9:1 by volume, containing 0.2 M HCl). The yields of the two major products, 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-propanone (ketol I) and 3-hydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-2-propanone (ketol II), as a percentage of residual lignins, decreased progressively with increasing decay. Even so, substantial yields of I and II were obtained from the decayed wood, suggesting that during decay a considerable amount of the lignin remaining in the wood was as yet unaltered (e. g. ∼50% at a 67% weight loss). This result indicates that lignin is degraded from exposed surfaces; the decreasing yields of I and II with decay show that the surfaces become progressively larger.

The Distribution of Lignin in Birch Wood as Determined by Ultraviolet Microscopy

The distribution of lignin in black spruce has been determined quantitatively by the study of 0.5 μm transverse sections in a UV microscope. The average lignin concentration in the compound middle lamella was about twice that in the secondary wall. The lignin concentration of the middle lamella at the cell corners of adjacent tracheids was nearly four times that in the secondary wall but the volume of the secondary wall was much greater than the volume of the middle lamella. Thus, for earlywood, 72% of the total lignin was in the secondary wall leaving only 28% in the compound middle lamella and cell corner middle lamella regions. The corresponding values for latewood were 82% and 18% respectively. Use of oblique longitudinal sections of 0.1 μm thick permitted the resolution of the compound middle lamella. The lignin concentration in the true middle lamella was found to be equal to that in the cell corner middle lamella and the primary wall lignin content to be about twice that in the secondary wall.

The acidic groups in wood and pulp as measured by ion exchange

AbstractThe ion‐exchange capacities were determined for a variety of wood samples consisting of both softwood and hardwood. The experiments revealed that considerably more acidic groups are present in heartwood than in sapwood. The capacity (carboxyl) values found for all samples were substantially lower than would be expected from the estimated uronic acid contents. This difference was more striking for hardwood than for softwood. After alkali treatment (pH 11.5, 64°C), the exchange capacity of the wood was increased considerably and this effect was more pronounced for hardwood than for softwood. This observation either indicates the presence of carboxylic acid estera and lactones or is attributable to an increased accessibility of carboxyls. Such an increase may occur in hardwood as a consequence of the deacetylation of xylan. In another series of experiments the effect of sulfonation was studied. Wood samples (Picea abies, Betula verrucosa, and Betula pubescens) were sulfonated at various pH values at 80 and 90°C. so that only small quantities of the wood substance were dissolved. In addition, the number of acidic groups was determined for a series of spruce and birch pulps with varying lignin contents. It was possible to distinguish between the carboxyl and sulfo groups by means of an ion‐exchange method developed for that purpose. The experiments revealed that the accessibility of carboxyl groups is considerably increased even after sulfonation at a low temperature. It also became apparent that most of the carboxyl groups are accessible even in pulps with relatively high lignin contents. The carboxyl values together with xylose analyses showed that the acidity of xylan remaining in pulp is substantially decreased during cooking. This decrease is more pronounced for birchwood than for sprucewood. Finally, it is evident from these experiments that sprucewood lignin is sulfonated to a markedly higher degree than birchwood lignin.