Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin 2: significance of oxidation reaction of lignin during oxygen delignification

The progress of lignin oxidation during oxygenalkali bleaching of pulp was evaluated by the method based on the difference between permanganate consumption of original pulp and that of the mixture of pulp and effluent after oxygen-alkali bleaching. By low-consistency oxygen bleaching of softwood kraft pulp, the permanganate consumption decreased very little. When the kappa number of the pulp was halved (from 25.4 to 13.4), the decrease in permanganate consumption of 1 g pulp was only 1.22ml of 0.02mol/l potassium permanganate. This value was smaller than that obtained for the oxygen-alkali treatment of a corresponding amount of isolated residual lignin, 6.40ml. This was not due to the slow oxidation of lignin in pulp but to the formation of permanganate-consuming substances from carbohydrates. Those newly formed substances cannot be oxidized by oxygen-alkali treatment. Taking these facts into account, lignin originally present in pulp was found to be oxidized well. Reduction of carbonyl groups in carbohydrates prevented the formation of such substances.Part of this paper was presented at the 10th ISWPC, Yokohama, June 1999; and at the 43rd Lignin Symposium, Fuchu, October 1998     

Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin I: method and its application to lignin oxidation

A new method is applied to evaluate the progress of the oxidation reaction of lignin during oxygen-alkali treatment. This method employs the difference in permanganate consumption of the sample before and after the oxygen-alkali treatment as an indication for the lignin oxidation. When kraft lignin and residual lignin isolated from unbleached softwood kraft pulp were subjected to oxygen-alkali treatment up to 6000min, the progress of the oxidation expressed by this method was separated into clearly distinguished three phases. During the first and second phases, the progress of oxidation was well correlated to the loss of methoxyl group and to the decrease in the yield of nitrobenzene oxidation products. The addition of Mn⁺ to the oxygen-alkali treatment depressed oxidation during the second phase partly and that during the third phase almost completely. Calculations based on the change in the permanganate consumption revealed that the oxidation during the first phase corresponded to 4.2 electrons abstracted from one lignin structural unit on average. The oxidation process by oxygen-alkali treatment was hypothetically attributed to the direct reaction between molecular oxygen and the phenolic unit of lignin, which mainly took place during the first phase, and to the autooxidation-type oxidation during the second and third phases.Part of this paper was presented at the 9th ISWPC, Montreal, June 1997; and at the 42nd Lignin Symposium, Sapporo, October 1997     

Kinetic analysis of color changes in cellulose during heat treatment

This paper deals with the kinetics of the color changes of cellulose during heat treatment. The color of cellulose heated at 90–180°C was measured by a spectrophotometer and expressed by CIELAB color parameters. The values of L* decreased and those of a*, b* and Δ E* _ab increased at all the treatment temperatures. Several kinetic models, namely, the zero-order, first-order, second-order and autocatalytic model, were applied to the changes in the color values. Furthermore, the results of kinetic analysis using the best-fit model were compared to the results obtained from conventional kinetic models. It was suggested that the kinetic analysis using the best-fit model was the better way to accurately predict color changes during heat treatment. The values of apparent activation energy calculated from the changes of L*, a*, b* and Δ E* _ab were 125, 124, 118 and 120 kJ/mol, respectively. These values were similar to the reported values calculated from other chemical or mechanical properties.     

Condensation of lignin during heating of wood

Summary The structural change of lignin during heating of wood was investigated quantitatively by a method combining nucleus exchange and nitrobenzene oxidation. Lignin modification during heating was mainly a diphenylmethane type condensation. About 40 and 75% of noncondensed units in protolignins were converted to diphenylmethane type units by heating of dry and wet wood meals up to 220 °C, respectively. On the other hand, during heating of modified lignin (dioxane lignin) various types of modifications in addition to diphenylmethane type condensation occurred. Lignin modification via the diphenylmethane type condensation was proposed as a new route for its utilization.     

Mechanical constraints on lignin deposition during lignification

Summary The ultrastructure of lignifying cell walls in Pinus radiata D.Don was investigated using potassium permanganate staining and transmission electron microscopy. Lignin deposition occurred at numerous discrete sites within various cell wall regions, suggesting the presence of some initiating agent at these sites. In the middle lamella region, lignin deposition occurred by addition of protolignin monomers to spherical particles of lignin. Lignification was completed by expansion of these spherical particles, initially forming irregular patterns of lignification followed by infilling of adjacent areas. In contrast, lignification in the secondary wall occurred by deposition of protolignin monomers onto the ends of expanding lignin lamellae between cellulose microfibrils leading to greatly elongated patches of lignin due to the greater rate of deposition along the microfibril axis compared to that across it. It is concluded that the cellulose matrix in which lignin deposition occurs, in the secondary wall, can exert a mechanical influence which limits the rate of lignin deposition in the direction perpendicular to the microfibril axis.     

Thermo characteristics of steam-exploded bamboo (Phyllostachys pubescens) lignin

Bamboo (Phyllostachys pubescens) internode was subjected to steam explosion treatment to produce an excellent fiber for binderless boards. Lignin was isolated from extract-free bamboo meal with Björkman’s procedure and steam-exploded pulp. The self binding-mechanism was discussed by scanning electron microscopy (SEM), thermo-gravimetry (TG), differential scanning calorimetry (DSC) and analytical ozonation. It is well-known that steam explosion treatment liberates lignin from the cell wall to the fiber surface, which is the most important component relevant to binderless board production. Results of TG and DSC analyses showed that steam-exploded bamboo pulp started mass loss at lower temperature compared to bamboo internode meal. The thermal softening temperature of lignin prepared from steam-exploded pulp was much lower than that of lignin prepared from extract-free bamboo meal. This suggests that intermonomer linkages of lignin, especially β-aryl-ether linkage which is the major intermonomer linkage of lignin, were cleaved during steam explosion treatment resulting in low molecular weight phenolic compounds. The cleavage of β-aryl-ether intermonomer linkage of lignin was also confirmed by ozonation analysis.     

Modeling of heat and mass transfer during high temperature treatment of aspen

A three-dimensional and unsteady-state mathematical model, which accounts for simultaneous heat and mass transfer taking place during the high temperature treatment of wood, has been developed. It was validated by comparing the predictions with the experimental data. In the model, the coupled heat and mass transfer equations proposed by Luikov are solved, and the temperature and moisture content profiles within wood are predicted as a function of time for different heating rates. For the model validation, an experimental study was carried out with aspen under different operating conditions. The samples were heated to high temperatures using a thermogravimetric system. The weight loss and the temperature distribution within the sample were monitored and registered during the experiment. The model can use constant or variable thermo-physical properties. The temperature and moisture content of the wood predicted by the model using variable properties were compared with those predicted by the same model using constant properties as well as with the experimental data. The experimental and model results are in good agreement, and it was shown that the accuracy of the model depends on the accuracy of the properties. After the model validation was completed, a parametric study was carried out.     

麦草碱木质素的氧化降解及产物特性的研究(I)

对不同氧化条件下,麦草氧化碱木质素的分子质量、酸溶木质素含量、酚羟基、羧基、甲氧基含量、表面活性的变化进行了研究.研究表明,当用碱量较高(60%,30%)时,其分子质量均一化程度较高.加入H2O2后分子质量＞10 000的高分子组分含量明显下降,但用碱量较低(10%.5%)时则变化不大,说明在02/H202氧化时碱有着明显作用.对酸溶木质素含量来说,也呈现出这一规律.木质素经氧化后,酚羟基含量升高,而羧基、甲氧基含量下降.在高用碱量条件(60%、30%)下,氧化木质素的表面张力下降较大,添加H202后下降更为明显.当用碱量为60%、H202用量10%时,氧化木质素4%水溶液的表面张力可由原木质素的46.8 mN/m降至38 8 mN/m     

The surface chemical constituent analysis of poplar fibrosis veneers during heat treatment

The scrimber is composed of the special elementary unit called fibrosis veneers. Study on chemical constituent changes of fibrosis veneers during heat treatment is helpful to expand the application areas of scrimbers. The objectives of this study were to investigate the effect of heat treatment on the chemical composition of poplar fibrosis veneers. The content changes of chemical composition and extractives after heat treatment were evaluated by chemical analysis. X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (NMR) were used to characterize the changes in the chemical structure of components. Untreated samples were also set for comparison. The results indicated that transformation of the material induced by this treatment led to an increase in the contents of lignin and extractives, while a decrease in those of holocellulose and α-cellulose. XPS spectroscopy results showed that the hemicelluloses and celluloses could be strongly affected by the atmosphere in the oven during the treatment. Relatively, the lignin was not very sensitive to the heating process to some extent. Solid-state NMR results showed that different degrees of transformations of the polymers took place during the heat treatment, resulting from the deacetylation of hemicelluloses, demethoxylation of lignin and changes in the cellulose structure.     

Application of the amount of oxygen consumption to the investigation of the oxidation mechanism of lignin during oxygen-alkali treatment

The dioxygen consumption by kraft lignin and several lignin model compounds during oxygen-alkali treatments were directly analyzed using a dioxygen fl owmeter. The average dioxygen consumption by 200 g of kraft lignin was about 3 moles. Because this value was as much as those obtained for monomeric phenolic lignin model compounds, guaiacol and vanillyl alcohol, it was postulated that not only phenolic but also nonphenolic moieties in kraft lignin are extensively oxidized. The dioxygen consumption by 0.5 moles (one equivalent of aromatic units) of a dimeric lignin model compound, guaiacylglycerol-β-guaiacyl ether (GG), was also similar to that for 1 mole of guaiacol and vanillyl alcohol, regardless of the type of the aromatic moiety, which supports the above postulation. The most plausible mechanism for the oxidation of nonphenolic moieties is the oxidation of side chains of residual β-O-4 substructures by active oxygen species. By this mechanism, nonphenolic moieties in kraft lignin and GG are converted into corresponding phenolic moieties, and the oxidation by dioxygen progresses. Part of this article was presented at the 13th International Symposium on Wood, Fiber, and Pulping Chemistry (13th ISWFPC), Auckland, New Zealand, May 2005     

Dynamics of microcrack propagation in hardwood during heat treatment investigated by synchrotron-based X-ray tomographic microscopy

The process of crack propagation in wood during pyrolysis is strongly linked to heterogeneities in its hierarchical porous structure. Fundamental understanding of this process is necessary for the analysis of the behavior of wood structural elements during fire exposure. Synchrotron-based X-ray tomographic microscopy combined with a recently developed laser-based furnace at the TOMCAT beamline of the Swiss Light Source provides a unique opportunity to study the heat-induced propagation of microcracks in hardwood in situ with high spatial and temporal resolutions. In this study, attention was focused on the 3D microstructure of beech and the interconnectivity between morphology and cracking patterns. It is shown that thermal cracks initiate mainly along the ray cells in hardwood and in the junction of seasonal growth layers. There is a clear indication of increased total porosity of the wood due to charring.     

葡萄果实转色期施用不同肥料对果实品质和成熟期的影响

研究肥料对葡萄果实品质和成熟期影响对于提高葡萄栽培的经济效益具有重要意义。本实验以巨峰葡萄为试材,研究葡萄转色期施用不同浓度磷酸二氢钾对果实品质和成熟期的影响。结果表明,T2处理的青颗粒为14.8%,且成熟期比对照早14天;3个处理的浓度水平都可使可溶性固形物总含量最高,风味最好;对于果实中酒石酸影响效果为T2T3T1,对于苹果酸含量的影响效果以此为T2T1T3;各处理中,以T2水平下葡萄果皮花青苷含量最高。     

Formation and chemical structures of acid-soluble lignin I: sulfuric acid treatment time and acid-soluble lignin content of hardwood

To elucidate the formation mechanism of acidsoluble lignin (ASL) formed in the Klason lignin determination, beech wood meals were treated with sulfuric acid (SA) under various conditions, and the ASL solution was extracted with CHC1₃. The results indicated the following: (1) wood components yielding ASL are dissolved in 72% SA during the initial stage; (2) the quantity of ASL is highest during the initial stage, then decreases with prolonged time of 72% SA treatment and finally reaches a constant value; (3) soluble lignin prepared by 72% SA treatment and subsequent standing in 3% SA again yield insoluble Klason lignin and ASL after boiling in 3% SA; and (4) about half the amount of ASL is dissolved in CHC1₃. The foregoing suggest that wood components yielding ASL are dissolved in 72% SA at the beginning and finally change to ASL after being subjected to depolymerization, hydrolysis, and other reactions. ASL may thus be composed of low-molecular-weight degradation products and hydrophilic derivatives of lignin.     

Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp

Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.Part of this paper was presented at the 46th Annual Meeting of the Japan Wood Research Society, Kumamoto, April 1996; the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June 1999; and the 67th Pulp and Paper Research Conference, Tokyo, June 2000     

Determination of optimum borate concentration for alleviating strength loss during heat treatment of wood

Based on the already established mitigating potentials of borate salt on the negative effects of heat treatment on the strength properties of wood (Awoyemi and Westermark 2005), the optimum concentration of the alkali buffer solution required to minimize strength loss was determined. Wood samples were impregnated with 0.1, 0.3 and 0.5 M sodium borate solution and exposed to heat treatment for 4 h at 200°C. The mitigating effect of borate salt on the degree of strength loss during heat treatment increases significantly with increasing concentration from 0.1 to 0.3 M. Increasing the concentration of sodium borate from 0.3 to 0.5 M did not produce significant differences in the degree of strength loss during heat treatment. The increase in the buffering effect observed with increasing concentration of the sodium borate preservative is more pronounced on the modulus of rupture than on the modulus of elasticity. It is evidenced therefore that the buffering effect of borate salt on the modulus of elasticity of wood exposed to heat treatment did not start significantly until the 0.3 M concentration is reached and further increase in concentration beyond this point did not produce any appreciable improvement in strength properties.     

Optimization of processing variables during heat treatment of oak (Quercus mongolica) wood

The properties of oak heat treated at temperatures of 160–220 °C, oxygen concentrations of 2–10 %, steam pressures of 0.1–0.4 MPa and treatment time of 2–4 h were investigated. Although modulus of elasticity (MOE), modulus of rupture (MOR) and equilibrium moisture content (EMC) of the heat-treated wood (HTW) were reduced, the value of $ \Updelta E^{*} $ was increased, and the dimensional stability [anti-swelling efficiency in radial (ASE-R), anti-humidity efficiency (AHE)] was improved considerably. Six regression equations (temperature, oxygen concentration, steam pressure and time as functions of MOE, MOR, ASE-R, AHE, EMC and $ \Updelta E^{*} $ ) were developed for the estimation and a nonlinear programming model was derived with operation research theory to obtain the most desirable HTW properties under some production constraints.     

Ready chemical conversion of acid hydrolysis lignin into water-soluble lignosulfonate III: Successive treatment of acid hydrolysis lignin and a lignin model compound by phenolation and arylsulfonation*

The chemical conversion of red pine sulfuric acid lignin (Klason lignin) (SAL) as an acid hydrolysis lignin sample to water-soluble arylsulfonates of lignin derivation (i.e., phenolized SAL) was investigated. Treatment of phenolized SAL with chlorosulfonic acid followed by alkali hydrolysis gave water-soluble sulfonated products with a sulfonic acid group on their aromatic nuclei quantitatively. The products possess 2.0 SO₃Na/C₉ C₆. In contrast, the content of sulfuric acid group in sulfonated SAL was only 0.33C₉. Chlorosulfonation of 1-guaiacyl-l-p-hydroxyphenylethane as a phenolized guaiacyl lignin model compound revealed that the sulfonyl chloride group was introduced at thepara position of an aromatic methoxyl group, theortho position of a phenolic hydroxyl group, or both.     

Active enzymes in wood chips and their action on lignin during outside storage

Summary Wood storage has a great influence on the efficiency of a pulpmill. Great problems arise when using outside chip storage, especially in processing hardwoods, in that hardwood chips discolorate after a few days, which is not the case with spruce chips. The causes of such a different behavior of beech and spruce were investigated. It could be shown that a sufficient amount of active peroxidase, malate dehydrogenase and oxygen are prerequisites for the formation of phenoxy radicals within the beech lignin. This causes formation of new chromophores that discolorize the wood. Sufficient amounts of such enzymes are present in beech wood after harvesting.