Spruce Wood Meal Research Articles

Spruce Woodmeal for Newsprint Applications: A Handsheet Study

This study shows that spruce woodmeal can be an alternative cellulosic-based wood additive for newsprint applications. This study used unbleached wood flour produced from Spruce sawdust, ground and sieved to a particle size of 20-40 µm, 40-70 µm, 70-120 µm and 200-500 µm.
 Woodmeal was added at levels of 2%, 4%, 6%, 8% and 10% based on oven dry fiber content. The basis weight of the newsprint handsheet manufactured was 80 g/m². The study revealed the following outcomes:
 Woodmeal with a particle size distribution of 20-40 µm had the highest density followed by woodmeal with 70–150 µm, 40-70 µm, and 200-500µm. Increasing the woodmeal amount resulted in higher porosity. Woodmeal with a particle size distribution of 20-40 µm gave the lowest porosity and a particle size of 40-70 µm gave the highest porosity.
 The Tensile index and burst index show decreasing values for the addition of all woodmeals and particle sizes. Woodmeal with strength additive and a particle size of 20 – 40 µm outperforms the other woodmeal types at additions of 2%, 4%, 6% and 8%. For woodmeal with a particle size of 70–150 µm at an addition of 2% and 4% an increased and similar burst index resulted for the handsheets.
 First pass retention and ash retention increased for all wood flours with a maximum at 92% and 81% respectively for the wood flour with a particle size of 40-70 µm.

Physicochemical Modeling for Pressurized Hot Water Extraction of Spruce Wood

The study of reaction kinetics and process modeling plays a vital role in the development and optimization of industrial processes. In this study, a physicochemical model is presented for pressurized hot water extraction of spruce wood meal to facilitate process development and optimization. The model takes into account several relevant phenomena during the extraction process, including acid–base reaction equilibrium, irreversible reaction kinetics, ion exchange, and mass transfer. The system is modeled by assuming two liquid phases, i.e., liquid external to wood fibers and fiber-bound liquid to enable inclusion of ion exchange. The nonideal behavior of the system (due to presence of ions) is considered by utilizing activities instead of concentrations. The scission of hemicellulose polymers into oligomers and monomers is modeled by a population balance approach of discretized categories. Model parameters are optimized by fitting the model output to experimental data reported in the literature. The presen...

Model for Degradation of Galactoglucomannan in Hot Water Extraction Conditions

A kinetic analysis is presented for the homogeneous degradation of galactoglucomannan (GGM) in hot water extraction conditions. In the experiments used for constructing the kinetic model, GGM extracted from spruce wood meal was treated at temperatures from 150 to 170 °C and in buffered pH 3.8–4.2. The hydrolysis of glycosidic bonds in GGM was modeled as a random process which is catalyzed by hydrogen ions. The real hydrogen ion concentration at the reaction temperatures was estimated. The Arrhenius equation was used to describe the temperature dependence of the hydrolysis rate and an activation energy of 102 kJ/mol was obtained for the reaction. The presented model predicts accurately the evolution of the molecular weight distribution with lower computational load than other similar models.

A novel method for the quantitative analysis of the water content in lignocellulosic material

A novel method for the determination of the water content in wood has been developed and experimentally tested. Based on the reaction of trimethylchlorosilane with various wood constituents and water, the generation of a by-product (hexamethyldisiloxane) was pursued and quantified via gas-chromatography and the water content was subsequently calculated back. The experiments were carried out with preconditioned spruce wood meal (particle sizes ranging between 60 and 140 microns) using water free solvents and reagents in a water free reaction atmosphere. The results showed that the investigated samples incorporated around 10 wt. % of water after preconditioning for 48 h.

Lignin Analysis by Permanganate Oxidation. I. Native Spruce Lignin

Permanganate oxidation has long been used to estimate the concentrations of uncondensed and condensed structures in phenolic lignin fractions. Four monomers and two dimers are normally quantified for softwood lignins and the actual yield of each is corrected for incomplete oxidation. Based on the analysis of several model compounds and lignin samples the correction factors were refined to give a better correlation between the original phenolic hydroxyl (PhOH) content and the total yield of selected products. An alkaline CuO pretreatment was used to hydrolyze most of the interunitary ether bonds in the lignin of spruce woodmeal. The PhOH content increased from 12/100 C 9 units to 69/100 C 9 units. A composition of approximately 55% uncondensed guaiacyls, 18% biphenyls and 14% β-5 was estimated from KMnO 4 oxidation of this sample.

Molecular Weight Distribution Study of Delignification of Spruce Wood Meal With Chloroacetic Acids

The amount of lignin removed from spruce wood meal at 50°C to 110°C with mono-, di-, and trichloroacetic acid, as well as its molecular weight (MW) distribution was studied. Trichloroacetic acid gives rise to the lowest Mn (2,000–4,000), the lowest Mw (4,500–8,000), the lowest upper MW limit (∼40,000), and the lowest polydispersity (1.5–3.0) of lignin. The removed lignin is split by the tested acids to different extents.

The mechanism of the M�ule colour reaction introduction of methylated syringyl nuclei into softwood lignin

Ezo spruce (Picea jezoensis) wood meal and milled wood lignin were successively reduced with sodium borohydride, methylated with methanol-HCl, oxidized with Fremy's salt, reduced with sodium dithionite, and methylated with diazomethane. Permanganate oxidation of the treated milled wood lignin showed that 0.08–0.1/C9 units of 3,4,5-trimethoxyphenyl groups were introduced into the softwood lignin. Although hardwood meal (beech, Fagus crenata) methylated with diazomethane gave a purple-red colour with the Maule test, the treated softwood meal gave only a dark brown colour. The aromatic nuclei of lignin were broken down by the Maule treatment. The consumption of permanganate by treated softwood lignin was higher than by hardwood lignin, which suggests that the guaiacyl nuclei were broken down severely. It is proposed that the purple-red colour obtained from methylated hardwood lignin with the Maule colour test is generated by reaction of syringyl groups which were liberated by β-ether cleavage under the permanganate oxidation conditions.

New aspects in cationization of lignocellulose materials. VIII. Modification of immitted spruce wood with quarternary ammonium groups

AbstractImmitted spruce wood meal (ISWM) was modified with 3‐chlor‐2‐hydroxypropyltrimethyl‐ammoniuchloride (CHMAC) or 1,3‐bis(3‐chlor‐2‐hydroxypropyl)imidazoliumhydrogensulphate (BCHIHS) in alkaline medium. The obtained material was gradually extracted with water and 5% NaOH. The yields of water‐soluble hemicelluloses modified with quarternary ammonium groups were lower in comparison to healthy spruce material obtained under the same conditions but even more material could be obtained from ISWM‐holocellulose. The quantity of alkali‐soluble polysaccharides from ISWM was the same as obtained from undamaged spruce. The residues after alkali extractions are suitable ion exchangers with low solubility in dilute alkali solutions. The yields of extracts from material modified with BCHIHS were lower than yields of extracts from material modified with CHMAC because ISWM was crosslinked when alkylated with bifunctional chemicals.

New aspects in cationization of lignocellulose materials. VII. Modification of spruce wood meal with quarternary ammonium groups

Trimethylammonium-2-hydroxypropyl (TMAHP) derivatives of spruce wood meal (SWM) and holocellulose of this specia were prepared by the reaction of wood meal with 3-chlor-2-hydroxy-propyltrimethylammoniumchloride (CHMAC) in alkaline medium. The TMAHP samples were fractionated and yields and exchange capacity (Q) of individual fractions were compared with beech and aspen fractions obtained under the same conditions. As it is evident from 13C-NMR spectroscopy and GPC analysis the water soluble fraction from TMAHP–SWM consists only of lignin–saccharide degradation products. The NaOH extracts of TMAHP–SWM and TMAHP–holocellulose as well as the water-soluble fraction from TMAHP–holocellulose are polymeric materials. From TMAHP–SWM only 3.1% of alkali-soluble material could be extracted, while from TMAHP–holocellulose 15.7% of water-soluble and 7.9% of alkali-soluble materials were obtained.

針葉樹材および広葉樹材のアルカリ性サルファイト・キノン蒸解における脱リグニン速度 ソーダキノンおよびクラフト蒸解との比較

The delignification rate constants were calculated as observed (pseudo) first-order reactions, and the effects of [OH-] and [SO32-] on the rate constants were evaluated in the Salkaline sulfite cooking with and without DDA (1, 4-dihydro-9, 10-dihydroxy-anthracene sodium salt). The delignification rates were also compared with those for kraft and kraft-DDA cookings.In the alkaline sulfite-DDA cooking of spruce and beech wood meals under the same conditions, the delignification rate constants for beech were not necessarily higher than those for spruce wood meals. This is quite different from the general observation for the soda, soda-DDA, kraft, kraft-DDA cookings, in which beech is higher than spruce. Especially in the case of beech, the delignification was not accelerated when the sodium sulfite concentration was increased from 0.4 M to 0.8 M. The addition of DDA could increase the effect of [32-] on the delignification in the alkaline sulfite cooking while it was not the case for [SH-] in the kraft cooking. Total alkali charge was higher in the alkaline sulfite-DDA cooking than those in the soda-DDA, kraft, kraft-DDA cookings to have a given rate constant.

Residual Sugars in Klason Lignin

Abstract The Klason method–dissolution of carbohydrates in sulfuric acid–has been widely used for the determination of lignin content in woody materials. It was an unsolved problem, however, whether Klason lignin still contains carbohydrates. We observed previously that Klason lignin becomes almost completely soluble in water after ozone treatment. In this work, the residual sugar content of Klason lignin was determined on the basis of the above observation. Water-soluble lignin was prepared by ozone treatment (25 and 45 min) of finely-crushed Klason lignin obtained from spruce and birch wood meals. After hydrolysis with 2N-trifluoroacetic acid followed by sodium borohydride reduction, residual sugars were determined by GLC as their alditol acetates. Klason lignin ozonated for 25 min contained 0.75% and 0.95% neutral sugars for spruce and birch, respectively. Most of the residual sugars were derived from hemicelluloses. Because ozone degrades carbohydrates, the prolonged ozonation was found to decrease th...

Degradation of lignin by ozone. III. The fate of the carbohydrate matrix during the degradation of spruce protolignin by ozone

AbstractSolvent‐extracted spruce wood meal was ozonized in 45% aqueous acetic acid at room temperature. The ozone‐treated wood meal was then extracted with dilute alkali at 65°C for 1 h. Lignin, α‐cellulose, and hemicellulose content and the viscosities of the pulped wood‐meal samples were measured as a function of the time of ozonization. Results indicate that although the attack on the wood components by ozone is not selective in this medium cellulose and hemicelluloses are degraded slowly compared with lignin. Lignin degraded approximately four times faster than the carbohydrates. At the fiber liberation point the pulp retained 78% of the original hemicelluloses and about 90% of the α‐cellulose compared with 25% of the lignin. The pulp samples obtained during ozonization of the wood meal showed a slow decrease in the average degree of polymerization (DP); the limit reached near 350 was attributed to the inaccessibility of the ordered regions in native cellulose to ozone.

Studies on the Condensation of Lignins in Alkaline Media. Part III. The Formation of Stilbenes, Arylcoumarans and Diarylmethanes on Treatment of Spruce Wood Meal with Alkali and White Liquor in the Presence of Xylenols.

Studies on the Condensation of Lignins in Alkaline Media. Part III. The Formation of Stilbenes, Arylcoumarans and Diarylmethanes on Treatment of Spruce Wood Meal with Alkali and White Liquor in the Presence of Xylenols.

The Reactions of Lignin during Neutral Sulfite Pulping. Part VIII. Sulfonic Acids Isolated after Treatment of Spruce Wood Meal with Neutral Sulfite.

The Reactions of Lignin during Neutral Sulfite Pulping. Part VIII. Sulfonic Acids Isolated after Treatment of Spruce Wood Meal with Neutral Sulfite.

Modification of oxidized lignins with styrene

AbstractThe effect of original and ozonized lignins upon the polymerization of styrene was investigated. It was found that the unoxidized lignin prepared by hydrolysis of spruce wood meals with 42% HCl retards the thermal polymerization of styrene. The ozonization of HCl‐lignin leads to its chemical transformation during which two types of functional groups are formed: those inhibiting and those initiating the polymerization of styrene. Moreover, the polymerization of styrene in the presence of oxidized HCl‐lignin affords both homopolymer and grafted copolymer. The amount of the grafted copolymer depends upon the concentration of active oxygen in lignin formed during oxidation, upon the temperature of polymerization, and, finally, upon the kind and concentration of the solvent used in the polymerization system.

GAS–LIQUID CHROMATOGRAPHIC ANALYSIS OF LIGNIN OXIDATION PRODUCTS

The gas–liquid chromatographic separation of vanillin, syringaldehyde, and p-hydroxybenzaldehyde has been effected using a 15% Apiezon N on Fluoropak column at 220 °C. Using standard solutions of the reference compounds and measuring peak areas, the percentage composition of mixtures of milligram amounts of these aldehydes may be determined quantitatively to within 5%.The method has been applied to the quantitative analysis of the phenolic aldehydes resulting from the alkaline nitrobenzene oxidation of aspen and spruce wood and wheat straw meals as well as the lignins isolated from these same plant materials. The results are reproducible and generally in good agreement with those reported earlier for similar lignified substances as determined using the spectrophotometer method of Stone and Blundell.

THE ISOLATION AND PROPERTIES OF LIGNINS OBTAINED BY THE ACIDOLYSIS OF SPRUCE AND ASPEN WOODS IN DIOXANE–WATER MEDIUM

A study has been made of the isolation of a lignin fraction from spruce and aspen wood meals using a low temperature (90–95 °C) acidolysis involving a dioxane–water (9:1) solvent medium containing the equivalent of 0.2 N hydrochloric acid. The effect of extraction time on the yield of precipitated lignin and ether-soluble material, and on the methoxyl content of these products, was investigated. For both species prolonged extraction times led to greater yields of lignin with lower methoxyl content.Further acidolysis of isolated spruce lignin led to no significant loss of methoxyl indicating the stability of this group to these reaction conditions. With increasing times of acidolysis of the aspen wood, a slow rise in the carbon–methyl/methoxyl ratio was observed for the isolated lignins. This is in agreement with earlier findings for the spruce lignin. The yields of vanillin and syringaldehyde from aspen lignin on alkaline nitrobenzene oxidation were much less than those from wood meal, and the relative yield of syringaldehyde was higher.It is suggested that this type of lignin may be only mildly modified during extraction and hence suitable for subsequent chemical investigation. The significance of the findings is discussed.

前スルフォン化エゾ松木粉のヒドロキシルアミン共存エタノリシス反應及びリグノオキシムスルフォン酸に就て

Each 20g of presulphonated spruce wood meal (solid lignosulphonic acid; Klason lignin and sulphur content are 25.2% and 0.9%, respectively) was treated with 200 cc of 3% ethanolic HCl and 4.2g NH3OH•HCl in boiling water bath during 1.5_??_28 hrs. After 10_??_28 hrs., about 60% of lignin was dissolved. When ethanolic filtrates were introduced in 5l H2O, light yellow flocculent precipitates (α) were formed. By the continuous extractions of aqueous filtrates with ether and evaporation of ether, brown syrups (β) were obtained. Average -OCH3, nitrogen and sulphur contents of α (β) are 15.86, 1.82 and 1.66%respect-ively (13.85, 7.25 and 0.92%). Therefore, their mole ratio in a (β) is 5.1:1.3:0.5 (4.5:5.2:0.3). From the results of the colorimetric determination of free NH2OH and oxime by Navak-Wilson's method [J. Bacteriology, 55, 517 (1948)], and of the potentiometric titrations of α, it is confirmed that nitrogen of α is oxime-form, and α is amphorite [HO3S-L(OCH3)7•(OC2H5)•(=NOH)2, isoelectric point: pH 4.5], having acidic (-SO3H) and basic groups (=NOH). Therefore, α (β) was designated, by the author, as α (β)-lignoximesulphonic acid. From results above mentioned, it is assumed that lignin molecule in presulphonated wood meal (solid lignosulphonic acid) has. carbonyl group and may be connecting with each other or with carbohydrate by means of acetal-linkage. It is supposed that β is similar in reference to these charaters.

固状リグノスルフォン酸生成(初期スルフォン化)反應の動力學的研究 (その1)

As the preliminary experiment for the kinetics of the formation of solid lignosulphonic acid (the first stage of the sulphite cooking on the Hägglund's theory), spruce wood meal (100 mesh, extracted with alcohol-benzene) was cooked with the following liquors at 135°, 0 to 5 hrs; (A) 15% Na2SO3 (pH 9.0), (B) 12% Na2SO3+3%NaHSO3 (pH 6.3), (C) 15% NaHSO3 (pH 4.4) and (D) neutral buffer solution (NaOH-KH2PO4; pH 7.0). The amounts of resoluted lignin in 5 hrs. cooking with liquors (A)_??_(C) were 3_??_6% of dry wood meal. The lowest amount was for the cooking with the liquor (B). On the other hand, there was no difference among first stage cookings with three liquors in relation to the inactivation of lignin for the second stage delignification (cooking with industrial cooking liquors). Consequently, the author would use the liquor (B) for the study of the kinetics of the formation of solid lignosulphonic acid. The author recognized in the determination of lignin with chlorine-water at 0°C (OKADA's method), the pretreatment of the coarse wood meal with 5% NaOH solution in boiling water bath (1 hr.) was the most adequate in order to let chlorine-water penetrate into wood meal.

固状リグノスルフォン酸生成(初期スルフォン化)反應の動力學的研究(其のII)

The kinetics of the formation of solid lignosulphonic acid (the sulphonation in the first stage of sulphite cooking) was carried out using the extracted spruce wood meal (100 mesh) and 12%Na2SO3+3%NaHSO3 solution (pH 6.3) as cooking liquor (liquor ratio 1:10) at 97°, 120° and 137°. From the analysis of the cooking results the sulphonation in the first stage of sulphite cooking are separated into two different sulphonation reactions. If they are treated separately, both of them can be treated strictly as the first order reaction. One reaction (X-reaction) is very fast, and the other (Z-reaction) is slow. The content of the active group (S-group) sulphonated in the first stage of sulphite cooking was 3.8% in lignin, if it were represented as sulphur content. S-group is separated into two groups; X- and Z-groups are sulphonated in X- and Z-reactions, respectively. Their contents are same; 1.90%. The activation energies (temperature coefficients per 10°C. in range 95°_??_135°) of X- and Z-reactions are 16.5 and 35 Cal (1.74 and 3.22), respectively. It is supposed that X-group is a bare active group in the lignin molecule, such as -OH in vanillyl alcohol, and Z-group is masked in some form, such as in weak linkage with carbohydrates.