Benzylated pulps from sugar cane bagasse

An optimized ethanol/water process has been employed for the pulping of fibres from sugar cane bagasse. After pretreatment with aqueous NaOH, unbleached pulps were subjected to benzylation at 110 °C for different periods of time. The resulting purified products were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and infrared spectroscopy (IR). The results showed that benzylation proceeded to various extents depending on the reaction time, as assessed by weight gain. During the first 3 h, a loss of mass was observed due to the occurrence of benzylation of low molecular weight polyoses, which were eliminated in the purification step. After that period of time a drastic weight increase was observed probably because crystalline regions had developed. The samples with low degrees of benzylation were insoluble, whereas the more benzylated counterparts showed limited solubility in THF. Partially soluble samples and a completely soluble one showed very different GPC elution profiles. This may be attributed to the efficiency of the pre treatment which, in the latter case, employed more concentrated alkali. Thermogravimetric analyses showed that all samples were degraded above 310 °C. Glass transition temperatures ranged between 42 °C and 65 °C, increasing as the extent of benzylation increased This revised version was published online in August 2006 with corrections to the Cover Date.     

灰色多层次综合评判在柳树材性分析中的应用

用灰色关联度与层次分析（ＡＨＰ）法选出了柳树作矿柱和造纸用材不同无性系的优良品种，其结果是：作造纸用材Ｊ９０３＞Ｊ７９９＞Ｊ１７２＞Ｊ３０８＞Ｊ７９５＞Ｊ８０２，作矿柱用材Ｊ９０３＞Ｊ７９９＞Ｊ３０８＞Ｊ１７２＞Ｊ７９５＞Ｊ８０２，为木材工业的发展进一步提供了信息和科学根据。     

Pretreatment with ammonia water for enzymatic hydrolysis of corn husk, bagasse, and switchgrass

Bagasse, corn husk, and switchgrass were pretreated with ammonia water to enhance enzymatic hydrolysis. The sample (2 g) was mixed with 1–6 mL ammonia water (25–28% ammonia) and autoclaved at 120°C for 20 min. After treatment, the product was vacuum-dried to remove ammonia gas. The dried solid could be used immediately in the enzymatic hydrolysis without washing. The enzymatic hydrolysis was effectively improved with more than 0.5 and 1 mL ammonia water/g for corn husk and bagasse, respectively. In bagasse, glucose, xylose, and xylobiose were the main products. The adsorption of CMCase and xylanase was related to the initial rate of enzymatic hydrolysis. In corn husks, arabinoxylan extracted by pretreatment was substantially unhydrolyzed because of the high ratio of arabinose to xylose (0.6). The carbohydrate yields from cellulose and hemicellulose were 72.9% and 82.4% in bagasse, and 86.2% and 91.9% in corn husk, respectively. The ammonia/water pretreatment also benefited from switchgrass (Miscanthus sinensis and Solidago altissima L.) hydrolysis.     

Enzymatic and alkaline treatments of hardwood dissolving pulp

Dissolving pulp was solubilized in 9% NaOH, resulting in 32% solubilization of the pulp. Most of the pulp hemicelluloses were solubilized during this treatment. During the alkaline treatment the cellulose crystalline form was converted from cellulose I to cellulose II. The alkaline insoluble residue was further treated with cellulases in order to render it more alkaline soluble (two-step process). The cellulose II was readily hydrolysed by Trichoderma reesei endoglucanases. Considerably higher hydrolysis yields and lower viscosities were obtained in the hydrolysis of the alkaline insoluble residue as compared with the original pulp. Compared with direct enzymatic treatment with subsequent solubilization in alkali, the overall alkaline solubility of the two-step process was slightly higher at the same enzyme dosage. However, when compared at the same hydrolysis levels, slightly lower overall alkaline solubilities were obtained in the two-step method. 0969--0239 © 1998 Black ie Academic & Professional     

A multivariate characterization of crystal transformations of cellulose

A spectroscopic study of cellulose transformation processes, such as alkali treatment and annealing, showed that, in combination with multivariate data analysis techniques, a detailed understanding of the crystalline transformation processes could be reached.¹³C cross-polarization magic-angle spinning (CPMAS) NMR and near-infrared (NIR) spectroscopy of cotton linters and softwood pulps analysed during the processing revealed information, after data reduction using principal components data analysis, that could be connected to structural changes of the cellulose polymorphs. The data showed that alkali treatment of cotton linters led to a cellulose conversion from cellulose I to II, while annealing, both for linters and pulps, yielded a transformation from I to I.     

Fenton’s reagent-mediated degradation of residual Kraft black liquor

In this work, the effect of Fento’s reagent on the degradation of residual Kraft black liquor was investigated. The effect of Fenton’s reagent on the black liquor degradation was dependent on the concentration of H₂O₂. At low concentrations (5 and 15 mM) of H₂O₂, Fenton’s reagent caused the degradation of phenolic groups (6.8 and 44.8%, respectively), the reduction of reaction medium pH (18.2%), and the polymerization of black liquor lignin. At a high concentration (60 mM) of H₂O₂, Fenton’s reagent induced an extensive degradation of lignin (95–100%) and discoloration of the black liquor. In the presence of traces of iron, the addition of H₂O₂ alone induced mainly lignin fragmentation. In conclusion, Fenton’s reagent and H₂O₂ alone can degrade residual Kraft black liquor under acidic conditions at room temperature.     

Xylose reductase activity of Candida guilliermondii during xylitol production by fed-batch fermentation

Xylose reductase activity of Candida guilliermondii FTI 20037 was evaluated during xylitol production by fed-batch fermentation of sugarcane bagasse hydrolysate. A 2^4-1 fractional factorial design was used to select process variables. The xylose concentrations in the feeding solution (S _F ) and in the fermentor (S ₀), the pH, and the aeration rate were selected for optimization of this process, which will be undertaken in the near future. The best experimental result was achieved at S _F =45 g/L, S ₀=40 g/L, pH controlled at 6.0, and aeration rate of 1.2 vvm. Under these conditions, the xylose reductase activity was 0.81 U/mg of protein and xylitol production was 26.3 g/L, corresponding to a volumetric productivity of 0.55 g/(L·h) and a xylose xylitol yield factor of 0.68 g/g.     

A comparative CP/MAS 13C-NMR study of cellulose structure in spruce wood and kraft pulp

CP/MAS ¹³C-NMR spectroscopy in combination with spectral fitting was used to study the supermolecular structure of the cellulose fibril in spruce wood and spruce kraft pulp. During pulping, structures contributing to inaccessible surfaces in the wood cellulose are converted to the cellulose I allomorph, that is, the degree of order is increased. This increase is also accompanied by a conversion of cellulose I to cellulose I. Cellulose from wood composed of different cell types, that is, compression wood, juvenile wood, earlywood, latewood and normal wood exhibited a similar supermolecular structure. Assignments were made for signals from hemicellulose which contribute significantly to the spectral C-4 region (80–86 ppm) in kraft pulp spectra but substantially less to the corresponding region in wood spectra.     

The effect of Trichoderma reesei cellulases and hemicellulases on the paper technical properties of never-dried bleached kraft pulp

Four purified cellulases, a xylanase and mannanase from Trichoderma reesei were used to treat never-dried bleached pine kraft pulp prior to refining, and the effects on pulp properties were evaluated. The enzymatic treatments hydrolysed up to 0.8% of pulp dry weight. The results demonstrated that the individual cellulases have profoundly different modes of action in modifying pulp carbohydrates. This is especially clear when comparing their effects at the same level of hydrolysis. Pretreatment with cellobiohydrolases I (CBH I) and II (CBH II) had virtually no effect on the development of pulp properties during refining, except for a slight decrease in strength properties. On the contrary, endoglucanase I (EG I) and endoglucanase II (EG II) improved the beatability of the pulp as measured by Schopper--Riegler value, sheet density and Gurley air resistance. Of the endoglucanases, EG II was most effective in improving the beating response. The combinations of CBH I with EG I and EG II had similar effects on the pulp properties as the endoglucanases alone, although the amount of hydrolysed cellulose was increased. Pretreatments with xylanase or mannanase did not appear to modify the pulp properties. The same enzyme treatments which improved the beatability, however, slightly impaired the pulp strength, especially tear index at the enzyme dosages used. When compared at a given level of cellulose hydrolysis, the negative effect of EG II on strength properties was more pronounced compared with EG I. Thus, the exploitation of cellulases for fibre treatments requires careful optimization of both enzyme composition and dosage. Since the endoglucanases had no positive effect on the development of tensile strength, it is suggested that the explanation for the increased beating response is increased fibre breakage and formation of fines, rather than improved flexibilization. This revised version was published online in August 2006 with corrections to the Cover Date.