Elisabet Quintana

Studying the effects of laccase treatment in a softwood dissolving pulp: cellulose reactivity and crystallinity.

An enzymatic biobleaching sequence (LVAQPO) using a laccase from Trametes villosa in combination with violuric acid (VA) and then followed by a pressurized hydrogen peroxide treatment (PO) was developed and found to give high bleaching properties and meet dissolving pulp requirements: high brightness, low content of hemicellulose, satisfactory pulp reactivity, no significant cellulose degradation manifested by α-cellulose and HPLC, and brightness stability against moist heat ageing. The incorporation of a laccase-mediator system (LMS) to bleach sulphite pulps can be a good alternative to traditional bleaching processes since thermogravimetric analysis (TGA) showed that the laccase treatment prevented the adverse effect of hydrogen peroxide on fibre surface as observed during a conventional hydrogen peroxide bleaching treatment (PO). Although VA exhibited the best results in terms of bleaching properties, the performance of natural mediators, such as p-coumaric acid and syringaldehyde, was discussed in relation to changes in cellulose surface detected by TGA.

An enzyme-catalysed bleaching treatment to meet dissolving pulp characteristics for cellulose derivatives applications

Bleached cellulose with good end-properties (≈ 90% ISO brightness and 62% cellulose preservation) was obtained by using a totally chlorine-free biobleaching process (TCF). Unbleached sulphite cellulose was treated with Trametes villosa laccase in combination with violuric acid. This enzymatic stage (L) was followed by a chelating stage (Q) and then by a hydrogen peroxide stage reinforced with pressurized oxygen (Po), resulting to an overall LQPo sequence. The use of violuric acid was dictated by the results of a preliminary study, where the bleaching efficiency of various natural (syringaldehyde and p-coumaric acid) and synthetic mediators (violuric acid and 1-hydroxybenzotriazole) were assessed. The outstanding results obtained with laccase-violuric acid system fulfil most of the characteristics of commercial dissolving pulp, totally acceptable for viscose manufacturing or CMC derivatives, with the added advantage that the enzymatic treatment saved 2h of reaction time and about 70% of hydrogen peroxide consumption, relative to a conventional sequence (Po).

Cellulose oxidation by Laccase-TEMPO treatments

In this work, laccase-TEMPO (Lac-T) treatments were applied to bleached commercial dissolving pulp in order to introduce carbonyl and carboxyl groups, which were found to improve dry and wet strength-related properties. Also the solubility behavior towards xanthate reactions was assessed. The effect of a refining step (R) before the oxidative treatment, the absence or presence of oxygen pressure, TEMPO dose (2 or 8% oven dried pulp) and reaction time (8 or 20h) were thoroughly examined. Treatments conducted in the presence of oxygen pressure exhibited greater amount of functional groups. Introducing a pre-refining treatment resulted in similar functional groups but higher wet strength was achieved. Specifically, a high W/D strength ratio was observed, indicating that wet strength-related property was satisfactorily developed. Besides the fact that all Lac-T treatments caused severe cellulose degradation, no fiber strength loss was detected. In fact, all oxidized samples presented higher Wet Zero-Span Tensile Strength, mainly in R+ Lac-T (O2) sample, which suggested the formation of hemiacetal linkages between the new introduced aldehyde groups and available free hydroxyl groups resulting from fibrillation.

Assessing the environmental impact of biobleaching: effects of the operational conditions

The environmental impact of enzyme bleaching stages applied to oxygen-delignified eucalypt kraft pulp was assessed via the chemical oxygen demand (COD), color, absorbance spectrum, residual enzyme activity and Microtox toxicity of the effluents from a laccase-HBT (1-hydoxybenzotriazole) treatment. The influence of the laccase and HBT doses, and reaction time, on these effluent properties was also examined. The laccase dose was found to be the individual variable most strongly affecting COD, whereas the oxidized form of HBT was the main source of increased color and toxicity in the effluents. Moreover, it inactivated the enzyme. Oxidation of the mediator was very fast and essentially dependent on the laccase dose. Using the laccase-mediator treatment after a xylanase stage improved pulp properties without affecting effluent properties. This result holds great promise with a view to the industrial implementation of biobleaching sequences involving the two enzymes in the future.

Alternative chemo-enzymatic treatment for homogeneous and heterogeneous acetylation of wood fibers

Abstract A new chemo-enzymatic treatment is proposed to produce cellulosic fibers suitable for heterogeneous- or homogeneous-phase acetylation. The procedure included enzymatic (laccase–violuric acid) lignin removal from the precursor fibers (unbleached sulfite pulp) followed by hydrogen peroxide treatment. An optional intermediate stage included partial hydrolysis (endoglucanase) to increase fiber reactivity. The obtained “biobleached” fibers were acetylated in the heterogeneous phase with acetic anhydride in nonpolar solvents, yielding various acetyl group contents, depending on the severity of the reaction. The degree of acetylation was highly sensitive to the treatment conditions, mainly the acetic anhydride activity in the system. The results were compared to those obtained after acetylation of commercial, dissolving-grade fibers, used as reference. The effect of the inherent nature of the fibers tested were elucidated as far as hemicellulose content, fiber length, fine content and crystallinity. Acetyl group content of up to 24% were determined after heterogeneous reaction with the chemoenzymatic fibers. The substitution of hydroxyl groups by acetyl moieties resulted in a lower hydrophilicity, as assessed by measurement of the water contact angle. Homogeneous acetylation of the chemo-enzymatic and reference fibers resulted in relatively similar acetyl group content (up to 36 and 33%, respectively). These samples were soluble in acetone and produced transparent films (via solvent casting), with enhanced dry strength and lower hydrophilicity. Overall, it is concluded that the proposed chemo-enzymatic treatment is a feasible alternative for the production of fibers that are suitable for efficient acetylation.