Application of a modified rate equation to the acetylation of wood

A modified rate equation, in which the diffusion of reagent was taken into consideration, was proposed and applied to results reported previously for the acetylation of wood. The equation was fitted more successfully to the prolonged as well as the early stage of the reaction than a common first-order rate equation. Although the conclusions were virtually unchanged, the reliability was enhanced because reaction parameters such as the rate constant, ultimate extent of the reaction, and activation energy calculated for the modified equation were based on much more data than those reported previously. The equation proposed here may be applicable not only to acetylation but to other chemical modifications of cellulosic materials in heterogeneous systems.     

Contribution of lignin to the reactivity of wood in chemical modifications I: influence of delignification on acetylation

In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol. These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004     

Potassium acetate-catalyzed acetylation of wood at low temperatures II: vapor phase acetylation at room temperature

Ezomatsu wood blocks were impregnated with potassium acetate (KAc) and then exposed to acetic anhydride vapor at 25°C and 120°C. The KAc-impregnated wood was rapidly acetylated at 120°C, and only 6 min was needed to achieve 20% weight percent gain (WPG). The WPG increased with increasing catalyst loading (CL), but it turned to decrease above 20% CL probably because the diffusion of acetic anhydride vapor was hindered by excess KAc depositing in the cell lumina. Thus, careful control of CL is necessary in the vapor-phase acetylation. KAc was also effective in catalyzing the vapor-phase acetylation at 25°C: the KAc-impregnated wood attained 20% WPG within 7 days, whereas the WPG did not exceed 10% even after 1 month in the uncatalyzed system. Irrespective of treatment methods, the hygroscopicity of wood was reduced and its dimensional stability was improved with an increase of WPG. These results confirm that the use of KAc simplifies the acetylation process at room temperature with minimal loss of acetic anhydride.     

Swelling of acetylated wood I. Swelling in organic liquids

To investigate the affinity of acetylated wood for organic liquids, acetylated yezo spruce wood specimens were soaked in various liquids, and their swellings were compared to those of untreated specimens. The acetylated wood was rapidly and remarkably swollen in liquids having low hydrogen bonding power such as benzene and toluene in which the untreated wood was swollen only slightly or very slowly. On the other hand, the swollen volume of wood in water, ethylene glycol, and alcohols remained unchanged or slightly decreased after the acetylation. The effect of acetylation was greater in liquids having smaller solubility parameters. The easier penetration of aprotic organic liquids into the acetylated wood was considered to be due to the reduction of polarity and the scission of hydrogen bonds in the amorphous wood constituents where the hydrophilic hydroxyl groups were substituted by hydrophobic acetyl groups.     

Potassium acetate-catalyzed acetylation of wood at low temperatures I: simplified method using a mixed reagent

Ezomatsu wood blocks were acetylated in a mixture of acetic anhydride and acetic acid containing excess potassium acetate (KAc). The mixture method enabled rapid acetylation at 120°C: a 20% weight gain (weight percent gain; WPG) was achieved within 30 min while the WPG did not exceed 18% after 120 min of conventional uncatalyzed acetylation. At 40°C, however, a satisfactory WPG was not achieved with the mixture method because both the wood swelling and KAc concentration in the reagent solution were limited at that temperature. In addition, the antiswelling efficiency attained by the mixture method was irregularly low, probably because of nonuniform reaction involving shrinkage of the cell lumina. These results suggest that the mixture method is not advantageous for low-temperature acetylation, whereas it enables simple and rapid acetylation at high temperature.     

Dependence of reaction kinetics and physical and mechanical properties on the reaction systems of acetylation I: reaction kinetic aspects

The dependence of the reaction parameters of acetylation on the reaction mixture was compared among uncatalyzed, acetic anhydride-xylene mixed, and acetic anhydride-pyridine mixed solutions. Wood meal and blocks were used to examine the effect of sample size. A first-order rate equation was applied to the data, and a rate constant and leveling off value of weight gain (WG) were estimated. The rate-determining step was examined from the viewpoint of activation energy. The results were as follows: (1) Regarding the magnitude of the rate constant, the order was pyridine system > uncatalyzed system > xylene system. (2) The ultimate value of WG was lower in the uncatalyzed and xylene systems than the pyridine system, probably because of the swelling ability of pyridine. (3) The activation energies of acetylation estimated for wood meal were 120, 135, and 110kJ/mol for the uncatalyzed, xylene, and pyridine systems, respectively. (4) The characteristics of the diffusion-controlled reaction became marked when the acetylation was carried out in the pyridine system, at elevated temperature, and for wood blocks. Under these conditions, the supply of reagent to the reaction site might not be sufficient to fuel the reaction.Part of this report was represented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Swelling of acetylated wood II: effects of delignification on solvent adsorption of acetylated wood

To clarify the role of lignin in the affinities of acetylated wood for organic solvents, the effects of delignification on the solvent adsorption of acetylated wood were investigated. Acetylated wood meals rapidly adsorbed organic solvents that were hardly adsorbed by unmodified wood. For nonpolar and low-polarity organic solvents, a clear positive correlation was observed between the amount of adsorption and the lignin content. This indicated that acetylated lignin was responsible for the excellent affinities of acetylated wood for hydrophobic organic solvents. On the other hand, for lower alcohols and water, the amount of adsorption reduced with an increase in the lignin content. It was suggested that the adsorption of such polar solvents was dominated by insufficiently acetylated hydrophilic polysaccharides.     

Empirical analysis on influencing factors of waste paper recovery rate in China

ABSTRACT

The research calculated the waste paper recovery rate, and analyzed the main factors influencing waste paper recovery rate in China with time series data from 1970 to 2012. The consequent recovery rate and utilization rate of waste paper show that the recovery of paper products has been experiencing a rapid growth in China, but it cannot meet the domestic need. The empirical analysis proves that demand is the main driver to stimulate the increase of waste paper recovery rate in China; the increased average GDP per capita and proportion of waste paper pulp are two other important factors; the increased urbanization rate does not exert significant influence. In the circumstance of insufficient timber supply, the policy of eliminating straw pulp capacities for paper-making indusrty improves the recovery rate of waste paper.     

影响木材运输船舶合理吨位的几个因素的分析

本文通过对影响木材运输船舶合理吨位几个主要因素及对五种船型吨位和运输方式的分析,指出在航道及船闸尺度允许的条件下,应选用尽可能大的船舶及船队尺度,以充分利用船闸平面尺度,提高船舶载货量,降低成本。同时指出闽江流域梯级渠化后。主要干支流采用500t级一轮二驳顶推船队及500t级机动驳一顶一船组的运输方式较经济合理。     

DETERMINE ON INITIAL DIMENSIONAL STABILITY OF CHEMICAL MODIFIED WOOD

Strain development along radial direction was continuously determined by D—200Linear Variable Differential Transformers(L.V.D.T).When a wood specimen was put into waterand begin to swell from absolute dry moisture content to the maximum.Experiment results showthat the differences of swelling with soaking time between untreated and treated wood specimens dueto uptaking water.It would also give an indication to the effectiveness of various chemicals on thedimensional stability of modified wood.ASE of modified wood samples with SA-EP,EP and SA were found to be better than MA-AGE.SA-EP had got the best effetiveness on dimensional stabili-ty in reducing the swelling.     

竹束、木束浸胶量影响因素分析

以3种状态的竹束和木束为原材料,研究分析在相同条件下,浸渍酚醛树脂胶黏剂固体含量以及浸胶时间对竹束和木束浸胶量的影响。结果表明:相同的条件下,竹束、木束酚醛树脂浸胶量随浸胶时间的增加变化不明显;在相同浸胶时间下,竹束、木束酚醛树脂浸胶量随酚醛树脂胶固体含量的不同而变化显著;确定竹束、木束适宜的浸胶时间和酚醛树脂胶固体含量分别为25 min和30%。     

红木家具企业如何提高红木材料利用率

近年来全球林木被大量的采伐,引发林木资源越来越短缺,使得红木原材料价格不断上涨,红木家具企业的生存发展受到极大的冲击。如何提高红木原材料利用率是红木家具企业发展的大事。     

Dimensional stability of wood acetylated with acetic anhydride solution of glucose pentaacetate

Five wood species were acetylated with acetic anhydride (AA) solution of glucose pentaacetate (GPA) at 120°C for 8h, and the effect of GPA on the dimensional stability of the acetylated wood was investigated. Some GPA was introduced into the wood cell wall during acetylation. The GPA remaining in the cell lumen penetrated the cell wall effectively after heating to more than 140°C for 10min. The bulking effects of GPA resulted in a 10%–30% increase in the anti-swelling efficiency of the acetylated wood with 20% GPA/AA solution in place of AA. Hydrophobic GPA did not deliquesce under highly humid conditions and it remained in the cell wall after boiling in water.Part of this paper was presented at the 51st Annual Meeting of the Japan Wood Research Society, Tokyo, April 1988     

Chemical modification of wood by anhydrides without solvents or catalysts

Acetylated, propionylated, butyrylated, isobutyrylated, and hexanoylated woods were prepared at several temperatures. The reaction rate, dimensional stability, and changes in the ratios of specific gravity and dimensions in the tangential and radial directions were estimated. The reaction rate of propionylation was slow at temperatures under 90°C but increased with the temperature. The butyrylated, isobutyrylated, and hexanoylated woods showed little or no weight percent gain (WPG) and little or no antiswelling efficiency (ASE) below 110°C even for 24h, but they achieved significant WPG and ASE values at 140°C with a longer reaction time. The acetylated, propionylated, and butyrylated woods showed almost the same values for dimensional stabilization efficiency based on WPG (DSE). The specific gravity and dimensions ratios for acetylated, propionylated, and butyrylated woods compared to those of untreated wood increased with an increase in WPG.     

试析影响路基压实的因素

分析影响路基压实的因素：土质、含水量、压实功能和地基强度。     

Effect of acetylation on the chemical composition of hornbeam (Carpinus betulus L.) in relation with the physical and mechanical properties

Common hornbeam (Carpinus betulus L.) is a highly underused wood species despite its great hardness, strength, wear-resistance and toughness. It is mainly used as firewood in Hungary because of its wood defects, irregular shape and low-dimensional stability. These wood defects and small breast height diameter result in a low yield. It is non-durable outdoors as it tends to turn grey, crack and be attacked by wood-decaying organisms. Indoors it lasts for hundreds of years. One technology that could improve the stability and durability properties is acetylation. Hornbeam was acetylated with the Accoya® method under industrial conditions. The aim of this research was the assessment of acetylation affecting the chemical properties of hornbeam wood and how these are related to the change in physical and mechanical properties. Main wood constituents (cellulose, hemicellulose, Klason lignin, extractives and ash content) were determined and compared. Chemical parameters related to the degradation of structural polymers were also evaluated (total phenolic and soluble carbohydrate contents, pH and buffering capacity, furfural, levulinic acid, formic acid, acetic acid). Structural changes in acetylated wood and in the Klason lignin fraction were also assessed using FTIR spectroscopy.     

木材液相乙酰化处理及处理材尺寸稳定性和耐腐性的研究

本文论述了马尾松、白桦和青杨三种木材的液相乙酰化条件及各种乙酰化木材的尺才稳定性和耐菌腐能力。以乙酸酐和二甲苯为处理液,反应的最佳条件是:温度120℃,时间7到11小时,乙酸酑与二甲苯配比1:1。当处理试样的增重到15%时,抗收缩率可达60%以上。增重为11.75—17.98%的不同处理试块,其耐菌腐能力可提高3—34倍。     

FTIR-PAS study of light-induced changes in the surface of acetylated or polyethylene glycol-impregnated wood

The objective of this study was to characterize the surface changes in acetylated and polyethylene glycol (PEG)-impregnated wood caused during light irradiation by Fourier transformed infrared photoacoustic spectroscopy analysis to determine their effects on the reduction of light deterioration. Light irradiation made the color of the chemically modified wood lighter or more vivid, whereas it deepened the color of the untreated wood. The color difference during light irradiation was less in the chemically modified wood than the untreated wood. The color difference of PEG-impregnated wood increased with increasing irradiation time. The light irradiation generated much carbonyl and significantly degraded lignin in the untreated wood. The generation of carbonyl and lignin degradation diminished in the acetylated wood in comparison with the untreated wood, indicating that acetylation restrained the photochemical degradation of wood. Deacetylation did not occur during light irradiation of the acetylated wood. The PEG impregnation decreased the generation of carbonyl and degradation of lignin during light irradiation. However, the irradiation occurred a little photochemical degradation of PEG, generating the carbonyl. Therefore, longer light irradiation should increase the degradation of PEG, thus reducing the effect of treatment. The correlation between the color difference and lignin degradation was high, indicating that the color changes during light irradiation significantly depended on lignin degradation. The chemical modification reduced the degradation of lignin and consequently decreased the color difference. Some of the compounds containing the carbonyl generated during light irradiation were water-soluble.This paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

不同处理方法对杨树木材压缩变形恢复率的研究

采用加热和水蒸气处理方法对人工林杨树木材进行压缩变形恢复率的研究,目的是为了改善人工林软质木材的材性,提高其尺寸稳定性。结果表明:加热和水蒸气处理都是固定人工林木材压缩变形的有效方法;在处理温度相同时,水蒸气处理方法只需要4 min或8 min,而高温加热处理需要10 h或20 h。水蒸气处理方法更加经济。