Juan C. Villar

Lignin Changes after Steam Explosion and Laccase-Mediator Treatment of Eucalyptus Wood Chips

Eucalyptus globulus chips were steam exploded followed by treatment with a laccase-mediator system (LMS) under different experimental conditions. Removal of hemicelluloses and, to a lesser extent, lignin was observed. Thermogravimetic analyses of whole meal obtained from chips before and after steam explosion indicated an increase in lignin degradation temperature due to lignin condensation. In contrast, application of LMS treatment caused a reduction in lignin and polysaccharide degradation temperatures. Lignins were isolated from wood samples before and after each treatment and analyzed by 2D NMR and (13)C NMR. An increase in carboxyl and phenolic hydroxyl groups and a significant decrease in β-O-4 structures were found in steam-exploded samples. The most relevant changes observed after laccase treatment were increased secondary OH and degree of condensation.

Kraft pulp biobleaching using an extracellular enzymatic fluid produced by Pycnoporus sanguineus.

The aim of this work was to obtain a LMS pre-treatment applicable to industrial TCF bleaching. Kraft pulp from Eucalyptus globulus was treated at 40 degrees C/pH 3 and 60 degrees C/pH 5 for 1h using an extracellular fluid enriched in laccase produced by Pycnoporus sanguineus and acetosyringone as mediator (HBT was used as a control mediator) (L). Alkaline extraction (E) and hydrogen peroxide (P) stages were then assayed. The LEP alternative was an efficient sequence to bleach kraft pulp since the enzymatic pre-treatment boosted the subsequent chemical bleaching. The best L pre-treatment was obtained with laccase-acetosyringone at 40 degrees C/pH 3. It reduces kappa number and hexenuronic acids, increases pulp viscosity, lowers hydrogen peroxide consumption down to an 87.4% (94.0% without L) and enhances brightness up to a 59% ISO (51% ISO without L).

Characterization of purified bacterial cellulose focused on its use on paper restoration

Bacterial cellulose (BC) synthesized by Gluconacetobacter sucrofermentans CECT 7291 seems to be a good option for the restoration of degraded paper. In this work BC layers are cultivated and purified by two different methods: an alkaline treatment when the culture media contains ethanol and a thermal treatment if the media is free from ethanol. The main goal of these tests was the characterization of BC layers measured in terms of tear and burst indexes, optical properties, SEM, X-ray diffraction, FTIR, degree of polymerization, static and dynamic contact angles, and mercury intrusion porosimetry. The BC layers were also evaluated in the same terms after an aging treatment. Results showed that BC has got high crystallinity index, low internal porosity, good mechanical properties and high stability over time, especially when purified by the alkaline treatment. These features make BC an adequate candidate for degraded paper reinforcement.

Integration of a kraft pulping mill into a forest biorefinery: Pre-extraction of hemicellulose by steam explosion versus steam treatment

Growing interest in alternative and renewable energy sources has brought increasing attention to the integration of a pulp mill into a forest biorefinery, where other products could be produced in addition to pulp. To achieve this goal, hemicelluloses were extracted, either by steam explosion or by steam treatment, from Eucalyptus globulus wood prior to pulping. The effects of both pre-treatments in the subsequent kraft pulping and paper strength were evaluated. Results showed a similar degree of hemicelluloses extraction with both options (32-67% of pentosans), which increased with the severity of the conditions applied. Although both pre-treatments increased delignification during pulping, steam explosion was significantly better: 12.9 kappa number vs 22.6 for similar steam unexploded pulps and 40.7 for control pulp. Finally, similar reductions in paper strength were found regardless of the type of treatment and conditions assayed, which is attributed to the increase of curled and kinked fibers.

Laccase production by Pycnoporus sanguineus under different culture conditions.

Pycnoporus sanguineus is a white‐rot fungus that produces ligninolytic enzymes such as laccases. These enzymes can endure temperatures as high as 60 °C and are useful for pulp bleaching, dye decolorization and phenolic degradation.

Enhancement of enzymatic saccharification of Eucalyptus globulus: Steam explosion versus steam treatment

Steam explosion and steam pre-treatment have proved capable of enhancing enzymatic saccharification of lignocellulosic materials. However, until now, these methods had not been compared under the same operational conditions and using the same raw material. Both pre-treatments lead to increased yields in the saccharification of Eucalyptus globulus; but results have been better with steam pre-treatments, despite the more accessible surface of exploded samples. The reason for this finding could be enzymatic inhibition: steam explosion causes a more extensive extraction of hemicelluloses and releases a greater amount of degradation products which can inhibit enzymatic action. Enzymatic inhibition is also dependent on the amount and chemical structure of lignin, which was also a contributing factor to the lower enzymatic yields obtained with the most severe pre-treatment. Thus, the highest yields (46.7% glucose and 73.4% xylose yields) were obtained after two cycle of steam treatment, of 5 and 3 min, at 183°C.

Combination of steam explosion and laccase-mediator treatments prior to Eucalyptus globulus kraft pulping.

The effect of a pretreatment consisting of steam explosion (SE) followed by a laccase mediator system (LMS) stage on Eucalyptus globulus kraft pulping has been evaluated and compared with fungal pretreatments. Pretreatment with SE and LMS was more efficient than pretreatments using Pycnoporus sanguineus and Trametes sp. I-62. Steam explosion not only improved the enzyme penetration into the wood chips and shortened the pulping process by 60%, but also extracted around 50% of the hemicelluloses which could be converted into value-added products. The optimal conditions for the LMS treatment were 3h, 3UA/g and 40°C. Compared to SE, the SE/LMS treatment yielded an increase in delignification of 13.9% without affecting pulp properties, provided a similar screened kraft yield, and reduced consumption of chemical reagents Na(2)S and NaOH by 11.5% and 6.3%, respectively. Therefore, SE/LMS is a promising pretreatment for converting the pulp mill into a forest bio-refinery.

Biobleaching of Eucalyptus globulus kraft pulps: Comparison between pulps obtained from exploded and non-exploded chips

The aim of this work was to evaluate the response to biobleaching of steam exploded kraft pulps and to compare the results with the controls. For this end, a laccase-mediator treatment using commercial laccase (Novozyme 51003) and a natural mediator (acetosyringone) were assayed, followed by alkaline extraction and hydrogen peroxide stages. Our approach resulted in exploded biobleached pulps with lower kappa number and improved optical properties compared to controls, even after subjecting pulps to accelerated ageing. Additionally, use of hydrogen peroxide was reduced. The LMS (laccase-mediator system) had a smaller impact on the properties of the bleached pulps and on hydrogen peroxide consumption than the steam explosion process did.

Use of bacterial cellulose in degraded paper restoration. Part II: application on real samples

Preservation of documentary heritage is one of the biggest challenges facing paper conservators today. The singular properties of bacterial cellulose (BC) lead us to propose to reinforce paper with BC sheets. In the first part of this study, the reinforcing capability of BC was tested on model papers of well-known fiber composition. The aim of the present study was to verify the suitability of rebuilding degraded old papers with BC. The degraded papers were characterized before and after the reinforcement. In addition, lined samples were characterized before and after an aging process in order to study the stability in time. The same methodology was used with Japanese paper (JP), a material commonly used by paper conservators, in order to compare both materials as reinforcement. Mechanical properties of paper lined with BC are as good as those obtained with JP. Papers lined with BC have more marked modifications on their optical properties than those restored with JP. Nevertheless, letters in books lined with BC are more legible. Moreover, only the papers restored with BC show high changes in porosity. The aging process leads to a slight decrement in burst index. Changes on tear index and optical properties with the aging process depend on the paper to be restored. This study suggests that BC improves deteriorated paper quality, without altering the information contained therein, and that this improvement is maintained over time. Hence, BC is a promising alternative material for the restoration of paper.

Effect of steam explosion and enzymatic pre-treatments on pulping and bleaching of Hesperaloe funifera.

A non-wood raw material with high potential for pulp and paper applications (Hesperaloe funifera) was subjected to a steam explosion pre-treatment, and the subsequent effect of this pretreatment on biopulping and biobleaching was studied. An increase in the delignification rate, bigger than that reported for autohydrolysis and acid hydrolysis pre-treatments, and a reduction in chemical consumption were found during kraft pulping of the exploded samples. However, biopulping with the laccase-mediator system (LMS) did not lead to a reduction in the kappa number in either non-exploded or exploded unbleached pulps. On the other hand, the steam explosion pretreatment boosted the advantages of the LMS pre-treatment (decrease in kappa number and increase in brightness) favored biobleaching, with a 53.1% delignification rate and a final brightness of 67% ISO. Finally, the steam explosion pre-treatment also improved the color properties of the bleached pulp and reduced the hydrogen peroxide consumption by 24.6%.