Research Articles

The biobleaching efficiency of xylanase and laccase enzymes was studied on kraft pulps from wood and nonwood based raw materials employed in the Indian paper industry. Treatment of these pulps with xylanase enzyme could result in improved properties, showing 2.0% ISO gain in pulp brightness and/or reducing the demand of chlorine-based bleach chemicals by up to 15% with simultaneous reduction of 20 to 25% in AOX generation in bleach effluents. Further, mill-scale trial results revealed that enzymatic prebleaching can be successfully employed with xylanases to reach the same bleach boosting efficacy. Laccase bleaching was also studied on hardwood pulp at a pH around 8.0, where most of the pulp mills in India are operating, in contrast to earlier studies on laccase enzyme bleaching, which were conducted at acidic pHs, i.e. 4.0 to 5.0. In case of laccase bleaching, interesting results were found wherein a bleach-boosting effect was observed even at pH 8.0. Further studies carried out with HOBT as mediator in comparison to the commonly used and expensive ABTS laccase mediator system (LMS) resulted in improvement of the bleaching efficiency with reduction in demand of chlorine dioxide by more than 35%. Potential for further reduction was indicated by the brightness gain, when compared with a control using the DE(p)D bleach sequence.

To investigate chemical and color changes of the polymeric constituents of black locust (Robinia pseudoacacia) wood during heat treatment, extractive-free wood flour was conditioned to 30% initial moisture content (MC) and heated for 24 h at 120 °C in either an oxygen or nitrogen atmosphere. The color change was measured using the CIELAB color system. Chemical changes of the wood components were determined by means of solid state cross-polarization/magic angle spinning 13C-nuclear magnetic resonance (CPMAS-13C-NMR), Fourier transform infrared (FTIR), diffuse reflectance UV-Vis (DRUV) spectroscopy, and elemental (CHN) analysis. The results showed that lightness (L*) decreased, while chromaticity indexes (a* and b*) and chroma (C*) increased after heat treatment.CHN analysis showed an increase in hydrogen and oxygen and a decrease in carbon content. NMR spectra confirmed the cleavage of the β-O-4 structure in the lignin, resulting in a decrease in etherified lignin units and an increase in phenolic structures. DRUV and FTIR spectra confirmed the formation of extensive conjugated structures, such as unsaturated ketones and quinones due to the cleavage of the lignin units. Formation of quinones can be attributed to heat treatment in the presence of oxygen.

The objective of this research was to study the changes in hardness and elastic modulus of wood cell walls treated with enzymes. Such changes greatly influence the properties of paper and wood composites. Two enzymes, hemicellulase and lipase, were selected for the treatment. Poplar samples (Populus euramevicana) were treated with hemicellulase, while samples of southern yellow pine (Pinus spp.) and Mongolia scotch pine (Pinus sylvestris L. var. mongolica Litv.) were treated with lipase. Mechanical properties of both treated samples were investigated by nanoindentation. The results showed some changes in the hardness and elastic modulus of the poplar cell wall treated by hemicellulase. Hardness and elastic modulus values of southern yellow pine and Mongolia scotch pine cell walls treated by lipase decreased with increasing amounts of the enzyme.

In order to improve the properties of thermomechanical pulp (TMP), the influences of the TEMPO (2,2,6,6-tetramethylpiperidyl-1-oxyl radical)-mediated oxidation on recycled TMP properties were investigated, and the impacts of recycling process on TEMPO-mediated oxidized TMP properties were studied as well. The results showed that TEMPO-mediated oxidation is an effective way to enhance the recycled TMP inter-fiber bonding dependent properties due to the introduction of carboxylic acid groups onto pulp, while the oxidation had some negative impacts on the tear index, zero span tensile index, and brightness. The oxidation-recycling (O-R) process had remarkable adverse impacts on TMP compared with the recycling-oxidation (R-O) process. The tensile, burst, tear strengths, as well as the zero-span tensile strength dropped sharply when oxidized TMP was recycled, and the physical strength properties decreased with the increasing recycling times. The opacity was improved after the O-R treatment, although the O-R treatment had an adverse impact on the pulp brightness.

Red maple, sweet gum, trembling aspen, red alder, and Eucalyptus globulus samples were pretreated with dilute sulfuric acid and green liquor before enzymatic saccharification. Substrates showed different levels of delignification and sugar recovery, depending on the applied pretreatments and the syringaldehyde/vanillin ratio (S/V). Three major conclusions were drawn in this research. First, lignin is the greatest contributor to recalcitrance of hardwood to enzymatic saccharification. Second, a high S/V ratio is a useful indicator of high delignification during a pretreatment process. Third, green liquor pretreatment is a promising pretreatment method because of a high delignification degree and sugar recovery. In addition, xylan also contributes to the recalcitrance of hardwoods toward enzymatic saccharification.

Carbohydrates that migrate to wood surfaces in sapwood during drying might influence properties such as mould susceptibility and colour. Sugars on the surface of Norway spruce boards during various heat treatments were studied. Samples (350mmx125mmx25mm) were double-stacked, facing sapwood-side outwards, and dried at 110oC to a target moisture content (MC) of 40%. Dried sub-samples (80 mm x 125 mm x 25 mm) were stacked in a similar way and further heated at 110oC and at 130oC for 12, 24, and 36 hours, respectively. Glucose, fructose, and sucrose as well as 5-hydroxymethylfurfural (HMF) and furfural in the sapwood surface layer of treated wood were analysed using HPLC (RI- and UV-detectors). Carbohydrates degraded to a lower extent at 110oC than at 130oC. Furfural and to a larger extent HMF increased with treatment period and temperature. Heat treatment led to a decrease in lightness and hue of the sapwood surface of sub-samples, while chroma increased somewhat. Furthermore, considerably faster degradation (within a few minutes) of the carbohydrates on the surface of the dried spruce boards was observed when single sub-samples were conductively hot pressed at 200oC. Treatment period and initial MC influenced the presence of the carbohydrates in wood surface as well as colour change (DEab) of the hot pressed sub-samples.

The effects of chemical modification of orange peel, bagasse, and a mixture of peel and bagasse for lead ion removal from aqueous medium were evaluated. The chemical modification of biomass was carried out with sodium hydroxide and citric acid to introduce carboxylate groups on the surface of the biomass. Infrared spectra confirmed the presence of carboxylate groups at 1735 cm-1. Adsorption isotherms performed by static adsorption experiments fitted very well to the linear Langmuir and Freundlich models. The experiments were carried out at pH 5 during 500 min of shaking time. Orange modified peel (O-MP) presented the highest adsorption capacity (84.5 mg g-1), notably higher than other biosorbents described in the literature. The kinetic studies showed that the process obeyed a pseudo-second-order rate expression, thus indicating a strong interaction between the biosorbent and adsorbate. It was found that the chemical modifications of sorbents promoted an adsorption energetically more spontaneous, as indicated by negative values of Gibbs free energy. On the other hand, desorption studies showed low leaching of lead ions from the biosorbent, thus confirming the strong interaction of lead ions and the biosorbent. The satisfactory maximum adsorption capacity obtained and negligible cost of biosorbent makes the sub-products of orange a reliable natural material for the removal of lead ions from aqueous effluents.

A simple approach to fabricate hollow silica nanorods is reported, using nanocrystalline cellulose (NCC) as templates. Uniform NCC with the length of ca. 100 nm and a diameter of ca. 10 nm were prepared by hydrolysis of microcrystalline cellulose (MCC) in strong sulfuric acid condition. NCC was used as a template to prepare a core-shell composite of silica and NCC. The sol-gel reaction of tetraethyl orthosilicate (TEOS) was employed to coat NCC with a nano thickness of silica in the presence of ammonia. Finally, hollow silica nanorods were obtained by calcination of the composite at 600°C to remove the organic cellulose template completely. The obtained hollow silica nanorods were found to have uniform size and shape: with a length of ca. 100 nm, an inner diameter close to the original diameter of NCC, and a thickness of around 10 to 15 nm. These results suggest that NCC is an excellent template for manufacturing nano hollow materials with uniform shape and size.

To further improve the expression level of recombinant xylanase in Pichia pastoris, the xynB gene, encoding the mature peptide from Aspergillus niger NL-1, was designed and synthesized based on the synonymous condon bias of P. pastoris and optimized G+C content. 155 nucleotides were changed, and the GC content decreased from 57.7% to 43.6%. The synthetic xynB was inserted into the pPICZaA and then integrated into P. pastoris GS115. The activity of the recombinant xylanase reached 1414.7 U/mL, induced with 0.8% methanol after 14-day cultivation at a temperature of 28oC in shake flasks, which was 267% higher than that of the native gene. Furthermore, the maximum xylanase activity of 20424.2 U/mL was obtained by high-density fermentation in a 5-L fermenter, which was the highest xylanase expression in P. pastoris yet reported. The recombinant xylanase had its optimal activity at a pH of 5.0 and temperature of 50oC. The recombinant xylanase was stable over a pH range of 4.5 to 8.0. Thus, this report provides an industrial means to produce the recombinant xylanase in P. pastoris.

Bi-layer hybrid biocomposites were fabricated by hand lay-up technique by reinforcing oil palm empty fruit bunch (EFB) and jute fibre mats with epoxy matrix. Hybrid composites were prepared by varying the relative weight fraction of the two fibres. The physical (void content, density, dimensional stability), and chemical resistant properties of hybrid composites were evaluated. When the jute fibre loading increased in hybrid composites, physical and chemical resistant properties of hybrid composites were enhanced. Void content of hybrid composites decreased with an increase in jute fibre loading because jute fibres showed better fibre/matrix interface bonding, which leads to a reduction in voids. The density of hybrid composite increased as the quantity of jute fibre loading increased. The hybridization of the jute fibres with EFB composite improved the dimensional stability of the hybrid composites. The performance of hybrid composites towards chemical reagents improved with an increase in jute fibre loading as compared to the EFB composite. The combination of oil palm EFB/jute fibres with epoxy matrix produced hybrid biocomposites material that is competitive to synthetic composites.