Effect of dose of xylanase on bleachability of sugarcane bagasse ethanol/water pulps

Pulps obtained from the ethanol/water cooking of sugarcane bagasse were bleached with the xylanase enzyme obtained from the fungus Thermomyces lanuginosus IOC-4145 and with the commercial enzyme Cartazyme HS from Sandoz. By changing the enzyme dose from 4.3 to 36 IU/g of pulp, kappa number and viscosity were maintained when the xylanase from T. lanuginosus was used. On the other hand, by using Cartazyme HS, kappa number decreased by 17%, reaching 35.5. This pulp was further extracted with NaOH without a decrease in viscosity (10 cP), and pulp with a kappa number of 13 was obtained. Xylanases had no significant effect on the ethanol/water pulps.     

Enzymatic pretreatment of kraft pulps from pinus radiata D don with xylanolytic complex of pénicillium canescens (CP1) fungi

After screening 14 strains exhibiting high xylanase activities,Penicillium canescens (CP1) andPenicillium janthinellum Biourge (CP2) strains were selected. The β-xylanases produced had an optimum temperature and pH of 50°C and 4.0, respectively. Using a bleaching sequence of D₁₀₀EP, D₈₀EP, and XD₈₀EP, the effluent color obtained with XD₈₀EP was lower for CP1 and CP2 than at the D₁₀₀ stage. The color was slightly higher at the XD₈₀EP stage than with the D₈₀EP sequence. In the final pulp obtained with XD₈₀EP pretreatment, the viscosity increase and the Kappa number was similar to that of D₁₀₀EP in the CP1 and CP2 strains. Brightness in the final pulp was slightly lower than that of control. The selectivity ratio was better for the CP1 and CP2 strains as compared to control. In the XD₈₀EP stage using xylanase extract from CP1 with a pulp consistency of 8 to 15%, the Kappa number was not changed, but the viscosity, brightness, and selectivity ratio were improved proportional to the rise in consistency and delignification. Breaking length, burst and tear index, porosity, and elongation, in the final paper did not change after enzymatic treatment. AOX decreased (26%) in the D₈₀ stage effluent as compared with D₁₀₀, whereas in the XD₈₀ stage diminished 42%. The enzymatic treatment with CP1 facilitates the lignin release, decreases the CL0₂ load by 20%, and reduces the AOX without any negative effects on the physical properties of the pulp and paper.     

Bleach Enhancement of Mixed Wood Pulp by Xylanase–Laccase Concoction Derived Through Co-culture Strategy

Mixed enzyme preparation having both xylanase and laccase activity was evaluated for its bleach enhancing ability of mixed wood pulp. The enzyme was produced through co-cultivation of mutant Penicillium oxalicum SAU_E-3.510 and Pleurotus ostreatus MTCC 1804 under solid-state fermentation. Bleaching of pulp with mixed enzyme had resulted into a notable decrease in kappa number and increased brightness as compared to xylanase alone. Analysis of bleaching conditions had denoted that 8 IU g⁻¹ of mixed enzyme preparation (xylanase/laccase, 22:1) had led into maximal removal of lignin from pulp when bleaching was performed at 10% pulp consistency (55 °C, pH 9.0) for 3 h. An overall improvement of 21%, 8%, 3%, and 5% respectively in kappa number, brightness, yellowness, and viscosity of pulp was achieved under derived bleaching conditions. Process of enzymatic bleaching was further ascertained by analyzing the changes occurring in polysaccharide and lignin by HPLC and FTIR. The UV absorption spectrum of the compounds released during enzymatic treatment had denoted a characteristic peak at 280 nm, indicating the presence of lignin in released coloring matter. The changes in fiber morphology following enzymatic delignification were studied by scanning electron microscopy.     

Selective degradation of lignin and elimination of HO radicals in pulps by O<Subscript>3</Subscript> and UV laser flash irradiation

HO^. radical is an aggressive reagent to abstract hydrogen from diverse substitutes and lead them to degradation, however, in reaction of active oxygen species with lignins, complex phenolic polymers, in dispersed lignocellulose such as pulp for environment-benign delignification, HO^. radicals should be eliminated as more as possible to prevent cellulose from unfavorably concomitant degradation. A reaction system of O₃ is constructed under UV laser flash irradiation, and HO^. radicals are controlled efficiently by it. A new mechanism is proposed, for the first time, that O^. radicals generated from reaction of O₃ with UV laser flash irradiation might be the contributor to scavenge HO^. radicals.     

ChemInform Abstract: Unusual Inorganic Biradicals: A Theoretical Analysis.

Quantum chemical calculations at the CASSCF level of theory on the O₃‐homologous molecules CX₂^2‐, NX₂^‐, X₃, OX₂, and FX₂⁺ (X: O, S, Se, Te, Po) indicate that the triatomic inorganic biradicals in the FX₂⁺ series have unusually high biradical character.     

Rigidity percolation model of polymer fracture

A theory of the fracture of polymers with network microstructure was developed that was based on the vector, or rigidity percolation (RP) model of Kantor and Webman, in which the modulus, E, is related to the lattice bond fraction p, via E ～ [p ? p_c]^τ. The Hamiltonian for the lattice was replaced by the strain energy density function of the bulk polymer, U = σ²/2E, where σ is the applied stress and p was expressed in terms of the lattice perfection via the bond density ν, with the entanglement molecular weight, ν = ρ/M_e and appropriate measures of crosslink density for rubber, thermosets, and carbon nanotubes. The stored mechanical energy, U, was released by the random fracture of νD_o[p ? p_c] over stressed hot bonds of energy D_o ≈ 330 kJ/mol. The polymer fractured critically when p approached the percolation threshold p_c, and the net solution was obtained as σ = (2EνD_o [p ? p_c])^1/2 with a fracture energy, G_1c ～ [p ? p_c]. The fracture strength of amorphous and semicrystalline polymers in the bulk was well described by, σ = [ED_oρ/16 M_e]^1/2, or σ ≈ 4.6 GPa/M_e^1/2. Fracture by disentanglement was found to occur in a finite molecular weight range, M_c < M < M*, where M*/M_c ≈ 8, such that the critical draw ratio, λ_c = (M/M_c)^1/2, gave the molecular weight dependence of the fracture as G_1c ～ [(M/M_c)^1/2 ? 1]². The critical entanglement molecular weight, M_c, is related to the percolation threshold, p_c, via M_c = M_e/(1 ? p_c). Fracture by bond rupture was in accord with Flory's suggestion, G/G* = [1 ? M_c/M], where G* is the maximum fracture energy. Fracture of an ideal rubber with p = 1 was determined not to occur without strain hardening at λ > 4, such that the maximum stress, σ = E (λ ? 1/λ) = 3.75E. The fracture properties of rubber were found to behave as σ ～ ν, σ ～ E, and G_1c ～ ν. For highly crosslinked thermosets, it was predicted that σ ～ (Eν)^1/2, σ ～ (X ? X_c)^1/2, and G_1c ～ ν^?1/2, where X is the degree of reaction of the crosslinking groups and X_c defines the gelation point. When applied to carbon nanotubes (SWNT and MWNT) of diameter d and hexagonal bond density ν = j/b², the nominal stress as a function of diameter is σ(d) = [16 ED_o(p ? p_c) j/b]^1/2/d ≈ 211/d (GPa.nm) and the critical force, F_c(d) ≈ 166 d (nN/nm), in which j = 1.15, b = 0.142 nm, E ≈ 1 Tpa, and D_o = 518 kJ/mol. For polymer interfaces with Σ chains per unit area of length L and width X ～ L^1/2, G_1c is then ～ [p ? p_c], where p ～ ΣL/X. The results predicted by the RP fracture model were in good agreement with a considerable body of fracture data for linear polymers, rubbers, thermosets, and carbon nanotubes. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 168–183, 2005     

对氨基苯甲酸热力学性质的量热和热分析研究

在80～400 K温区,用高精度全自动绝热量热仪测定了对氨基苯甲酸摩尔热容,得到摩尔热容随温度的变化的关系式为：     

Reuse of the xylanase enzyme in the biobleaching process of the sugarcane bagasse acetosolv pulp

In this work, pretreatment-enzymatic series of the bagasse-sugarcane pulp and alkaline extraction of enzyme treated pulp were carried out. In the pretreatment an enzyme dose was utilized and acetosolv pulp suspension of 3% (w/v) with different solvents (distilled water, 0.05 mol/L acetate buffer pH 5.5 and 0.05 mol/L phosphate buffer pH 7.25) stirred at 85 rpm for 2 or 4 h. The enzymes used were pulpzyme and cartazyme, both commercial. The accompaniment of the enzymatic activity was carried out through measurement in initial and finish of each enzymatic pretreatment. The xylanase-treated pulps and xylanase-alkaline-extracted pulps were analyzed regarding kappa number and viscosity. Pulpzyme recovery was better in phosphate buffered medium (84, 46, and 23% for first, second, and third enzymatic treatment, respectively) although in aqueous medium reached only 2% for every treatments. However, the improvement of pulp properties was evidenced only in aqueous medium for pulpzyme. Cartazyme recovery was similar for both solvents (water and acetate buffer), reaching values around 19% for first enzymatic treatment and 9% for second one. Nevertheless, the pulp properties increased only in acetate buffered medium.     

Analysis of pitch deposits produced in kraft pulp mills using a totally chlorine free bleaching sequence

Two organic deposits accumulated in a Kraft pulp mill during pulping of Eucalyptus globulus wood and throughout a TCF (totally chlorine free) bleaching sequence were characterized. One deposit was collected after cooking and an oxygen delignification stage while the other was collected after bleaching with hydrogen peroxide. The deposits were Soxhlet extracted with acetone, and the extracts redissolved in chloroform and subsequently analyzed by gas chromatography (GC) and GC-mass spectrometry (MS) using short and medium length high temperature capillary columns, respectively. On the other hand, the insoluble residues left after the acetone extraction were analyzed by Curie-point flash pyrolysis-GC-MS and by pyrolysis-methylation-GC-MS. The compounds identified in the deposits arise from the E. globulus wood lipophilic extractives that survive the pulping and bleaching processes. Triglycerides were completely hydrolyzed during the Kraft cooking and the fatty acids dissolved. Steroids (alcohols, hydrocarbons, ketones and esters) and waxes were the main components in the deposit collected after the oxygen delignification stage. After the bleaching with hydrogen peroxide, content of the waxes were reduced and fatty acids appeared. High amounts of fatty acids salts were also identified in the deposit collected after the oxygen stage, and in minor amounts in the deposit collected after hydrogen peroxide bleaching. In contrast, this deposit was mainly made up of high amounts of lignin-derived phenolic moieties.     

New process for producing cellulose acetate from wood in concentrated acetic acid

To explore further potential applications of acetic acid pulp, an investigation was conducted to develop a direct method for producing cellulose acetate from wood in combination with atmospheric acetic acid pulping. The process consists of delignification, totally chlorine-free bleaching, and esterification, with the concentrated acetic acid aqueous solution being used as only solvent throughout the process. The acetic acid pulp with kappa number of 30 and ISO brightness of 16 was bleached with 5% ozone on pulp to kappa number of 1.4 and brightness of 61. The resulting bleached pulp was further bleached with peracetic acid to kappa number of less than 1.0 and brightness of 68. The final bleached acetic acid pulp was acetylated with acetic anhydride in the concentrated acetic acid for 45 min to produce cellulose acetate with an apparent degree of substitution (DS) of 2.54. Although the product was lower grade compared with commercially available cellulose diacetate because it was prepared from the chemical pulp but not dissolving pulp, the product was almost soluble in acetone. Eventually, the DS of the acetone-soluble fraction was 2.62. The acetone solubility might be attributed to the original acetic acid pulp that had been partially acetylated during the pulping.     

Alkaline hydrogen peroxide bleaching of cellulose

A closed system bleaching apparatus was designed to determine the kinetics and effects of various factors on alkaline hydrogen peroxide bleaching of textile cellulose fabrics. It was confirmed that perhydroxyl anion is the primary bleaching moiety in alkaline hydrogen peroxide systems. The use of the apparatus in the measurement of fabric color, waste oxygen, and the subsequent calculation of hydroxyl ion, and molecular hydrogen peroxide confirmed that pH and titration of 'free' hydrogen peroxide in alkaline bleaching systems are not good indicators of bleaching mechanism. The role of the cellulose itself in the chemical bleaching system was determined. The rate of bleaching on cotton fabric was shown to be a first order reaction in concentration of perhydroxyl anion at 60 and 90°C. An activation energy of 17kcal/mole was estimated. Decomposition of H₂O₂ into waste oxygen was found to be second order kinetics.     

Potential of Thermo and Alkali Stable Xylanases from Thielaviopsis basicola (MTCC-1467) in Biobleaching of Wood Kraft Pulp

Thermo- and alkali-stable xylanases produced from Thielaviopsis basicola (MTCC-1467) on low-cost carbon source like rice straw were evaluated for their potential application in biobleaching of wood kraft pulp. Enzyme treatment at retention time of 240?min with 20?IU/gm of dried pulp resulted in ~85.2?% of reduction in kappa number. When compared to control, 110.8, 93, and 72.2?% of enhancement in brightness (percent International Organization of Standardization), whiteness, and fluorescence, respectively, were observed for enzyme-treated pulp. Spectroscopic analysis showed significant release of chromophoric compounds from enzyme-treated pulp. Furthermore, scanning electron microscope studies of unbleached and enzyme bleached pulp revealed the effectiveness of enzymatic treatment. The enzyme-treated pulp subjected to later stages of chemical bleaching resulted in 16?% decrease in chlorine consumption along with considerable reduction in chemical oxygen demand percentage (14.5?%) level of effluent. Various pulp properties like fiber length, fiber width, burst strength, burst index, tear strength, tear index, tensile strength, and breaking length were also significantly improved after enzyme treatment when compared to control.     

FT-Raman,FT-infrared and NIR spectroscopic characterization of oxygen-delignified kraft pulp treated with hydrogen peroxide under acidic and alkaline conditions

The effects of bleaching treatment of oxygen-delignified softwood kraft pulp with hydrogen peroxide under acidic and alkaline conditions were studied using standard technological techniques and spectroscopic analytical methods: near-infrared (NIR), Fourier-transform infrared (FTIR) and Fourier-transform (FT) Raman spectroscopies. Among the three tested spectroscopic techniques, NIR analysis appeared to be the most appropriate in terms of possible technological applications. The use of NIR spectroscopy combined with multivariate data analysis allowed to create models for pulp bleaching monitoring based on CIE L*a*b* measurements. Near-infrared and FTIR spectroscopic studies allowed differentiating between the effects of the acidic and alkaline peroxide bleaching stages, but failed in relation to the delignification process. The most representative bands in the FTIR and FT-Raman spectra in terms of delignification and chromophore removal exhibited no correlation with standard technological measurement results.     

Free‐volume variation in polyethylenes of different crystallinities: Positron lifetime,density, and X‐ray studies

High‐quality positron lifetime measurements (70 million total counts) are reported for polyethylenes (PEs) of different crystallinities (X_c = 3–82%). The specific volumes of the crystalline and amorphous phases (V_c and V_a, respectively) were estimated from density and wide‐angle X‐ray scattering (WAXS) experiments. Some samples (those with low values of X_c) were branched PEs, and those with high values of X_c were linear PEs for which X_c was varied with changes in the crystallization temperature. Both V_c and V_a increase with decreasing X_c in the range 0% ≤ X_c ≤ 56% (the branched PEs) but are constant for X_c ≥ 56% (the linear PEs). The lifetime spectra were analyzed with the MELT and LIFSPECFIT routines. Artifacts that can appear in the spectrum analysis were checked via an analysis of computer‐generated spectra. Four lifetime components appeared in all of the PEs; the two long‐lived ones are attributed to pick‐off annihilation of ortho‐positronium (o‐Ps) in crystalline regions (τ₃) and in holes of the amorphous phase (τ₄). With increasing X_c, τ₃ decreases from about 1.2 to 1 ns, τ₄ decreases from 3.0 to 2.5 ns, and the intensity I₄ decreases from 29 to 0%. An increase in I₃ from 6 to 12% was observed. A comparison with simulations shows that the true I₃ value approaches 0 for X_c → 0%. The decrease in I₄ is weaker than the increase in X_c; this leads to the conclusion that the apparent specific o‐Ps yield in the amorphous phase I₄^Xc increases with X_c. Possible reasons for this surprising results are discussed. The fractional free hole volume [h = (V_a ? V_occ)/V_a, where V_occ is the crystalline occupied volume] was estimated from density and WAXS results. Between X_c = 0 and 56%, h decreases from 0.151 to 0.090, but it does not change further above X_c = 56%. The mean size (v) of the local free volumes (holes) estimated from τ₄ decreases from 200 to 150 ų. The number density of holes (N_h) calculated from these values (N_h = h/v) also decreases from 0.8 to 0.6 nm^?3 in the range 0% ≤ X_c ≤ 56%. The values of V_a, V_c, h, and N_h increase with an increasing degree of branching but do not vary for linear PEs. The possible influence of a crystalline–amorphous interfacial phase (three‐phase model) on the observed lifetime parameters is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 65–81, 2002     

Ethanol/water pulp enzymatic pretreatment: Chemical and FTIR-PCA analyses

Pulps obtained from ethanol/water cooking of sugarcane bagasse were treated at different times using xylanase enzyme obtained from Thermomyces lanuginosus IOC-4145 or commercially (Cartazyme HS, Sandoz Products Ltd.). The enzyme dosage was 18 IU per g of dry pulp and the time varied from 4 h to 12 h. When xylanase from T. lanuginosus was used, the kappa number and viscosity improved independently of the processing time used (4 h, 8 h, and 12 h). After chemical evaluation, the obtained pulps were classified using Fourier Transformed Infra-Red Spectroscopy and Principal Component Analysis. The results showed that the first three principal components explained more than 90 % of the total variance of the pulp spectra.     

Methodology of analysis of unseparated mixtures: Error limits in estimating the total analyte concentration recalculated to a standard substance

In estimating the total concentration of similar analytes recalculated to a standard substance X_st, different sensitivities of their determination result in a systematic error δc, depending on the choice of X_st and the composition of the analyzed mixture. Two methods of predicting the limiting values of this error (δc _max), with and without the account of the properties of X_st are proposed and tested on model mixtures. The methods can be used if the total analytical signal linearly depends on the concentrations of analytes and is additive (spectrophotometry, conductometry, etc.). The value of δc _max is independent of the ratio of analytes concentrations in the sample. To reduce δc _max, one should equalize the sensitivities of the determination of all compounds of a given type and use analytes with medium sensitivities as X_st.     

Enzymatic bleaching of organosolv sugarcane bagasse pulps with recombinant xylanase of the fungus Humicola grisea and with commercial cartazyme HS xylanase

Organosolv (ethanol/water and acetosolv) pulps were treated with Humicola grisea var. thermoidea and compared with Cartazyme HS xylanase-treated pulp. The ethanol/water pulps treated with H. grisea had the same viscosity as unbleached pulps (8 cP). Ethanol/water pulps treated with Cartazyme had higher viscosity than H. grisea-treated pulps (12 cP). Acetosolv pulps treated with H. grisea and Cartazyme presented a reduction in viscosity; however, the pulps treated with H. grisea had a lower reduction in viscosity than Cartazyme-treated pulps. Ethanol/water pulps treated with H. grisea had a 23% reduction in kappa number in 4 and 8 h of treatment, compared with the unbleached pulps. Cartazyme-treated pulps had a kappa number similar to that of the control pulps for 4 h of treatment. Extending the treatment time to 12 h resulted in a reduction of 33%. The acetosolv pulp treated with H. grisea had a kappa number reduced to 23% in 4 h. Cartazyme treatment resulted in a reduction of 55 and 44% in kappa number for 4 and 8 h of treatment, respectively, when compared with control pulp. Extending the treatment time to 12 h decreased the kappa number 72%. Fourier transform infrared spectra and principal component analysis showed differences among unbleached, H. grisea-treated, and Cartazyme-treated pulps.     

Alkaline peroxide mechanical pulping of wheat straw with enzyme treatment

Alkaline peroxide mechanical pulping (APMP) of wheat straw with enzyme treatment was studied. Instead of direct enzyme pretreatment on wheat straw, an alternative treatment method was used, in which coarse pulps from refiner defibrated wheat straw rather than wheat straw were pretreated with a crude enzyme containing mainly xylanase, then impregnated with alkaline H₂O₂ solution and further refined. The optimum conditions of enzyme treatment were xylanase dosage of 10–15 IU/g of oven-dried wheat straw, 90 min, 50–60°C, pulp consistency of 5–10%, and initial pH of 5.0, and those for chemical impregnation were 6% NaOH, 70–80°C, 60–90 min, and 4 to 5% H₂O₂. Enzyme treatment improved pulpability of wheat straw by the APMP process, and final pulp quality such as brightness, breaking length, and burst index of pulp. Pulp from the APMP process with enzyme treatment could be bleached to a brightness of 70.5% ISO by two-stage H₂O₂ bleaching sequence with only 4% H₂O₂, and breaking length of the bleach pulp reached 4470 m.     

Crystallization kinetics of chalcogenide glass Se0.8 Te0.2

The crystallization kinetics of the chalcogenide glass Se_0.8Te_0.2 was studied by means of differential scanning calorimetry. The variation in partial area (X) with temperature (T) revealed that the transition from the amorphous to the crystalline phase occurs in two dimensions.Activation energies were determined for both the glass transition (E _t) and the crystallization (E _c).E _t was calculated from the variation inT _g with the heating rate (a).E _c was determined by three different methods: (i) variation inX withT, (ii) variation inT _p witha, and (iii) variation inT _c witha.E _t andE _c have values of 161.01±2.75 and 84.75 ±8.21 kJ/mol, respectively.

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Zusammenfassung Mittels DSC wurde die Kristallisierungskinetik des Chalkogenidglases Se_0.8Te_0.2 untersucht. Eine Änderung partieller Gebiete (X) mit der Temperatur (T) zeigte, daß der Übergang von der amorphen zur kristallinen Phase zweidimensional verläuft.Es wurde die Aktivierungsenergie sowohl für den Glasübergang (E _t) als auch für die Kristallisierung (E _c) bestimmt.E _t wurde mittels der Abhängigkeit vonT _g von der Aufheizgeschwindigkeit (a) ermittelt.E _c wurde auf drei verschiedene Wege bestimmt: (i) Änderung vonX in Abhängigkeit vonT, (ii) Änderung vonT _p in Abhängigkeit vona und (iii) Änderung vonT _c in Abhängigkeit vona. Die Werte vonE _t undE _c betragen 161.01±2.75 bzw. 84.75±8.21 kJ/mol.

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This work was partly supported by a Grant-in-Aid for Scientific Research from the GTZ GmbH and DAAD, W. Germany.     

Lignocellulosic fiber charge enhancement by catalytic oxidation during oxygen delignification

A series of one-stage oxygen delignification treatments with a softwood (SW) kraft pulp were studied employing 0.0-0.5% of a bismuth ruthenium pyrochlore oxide catalyst. The results demonstrated that a 0.09-0.18% charge of catalyst in an oxygen stage provided a 52.2-116.0% increase of carboxylic acid groups in the cellulosic component of kraft pulps without a significant decrease in fiber viscosity. A 3-factor at 3-level (L(9)3(3)) orthogonal experimental design was used to identify the main factors influencing acid group formation in pulp carbohydrates. The relative significance of experimental parameters for polysaccharide acid group formation was the molar equivalent NaOH, oxygen pressure, and finally, reaction temperature under the experimental conditions studied. The optimized reaction parameters for fiber charge development were shown to be 85-100 degrees C, 2.5% NaOH, and 800-960 kPa oxygen pressure. Pulps with higher fiber carboxylic acid content introduced by catalytic oxidation during oxygen delignification yielded a 10.9-33.7% increase in fiber charge after elemental chlorine free (ECF) pulp bleaching. The enhanced fiber charge resulted in 6.7-17.1% increase in paper sheet tensile index at comparable pulp viscosity.