Analytics for the modified kraft pulps

Tämän diplomityön tavoitteena on kehittää sopiva analyyttinen menetelmä muokatun kraft-sellukuidun substituutioasteen (DS) kvantitatiivista määrittämistä varten. Muokkauksella tarkoitetaan tässä yhteydessä joko kovalenttisesti tai adsorption avulla tapahtuvaa molekyylin kiinnittymistä sellukuidun pinnalle. Työn kirjallisuusosuudessa käsitellään lyhyesti eri muokkaustapoja ja yhdisteitä joiden avulla voidaan saavuttaa haluttuja ominaisuuksia sellusta valmistetuille lopputuotteille. Lisäksi kirjallisuusosuudessa käydään läpi käyttötarkoitukseen soveltuvimpia suoria ja epäsuoria analyysimenetelmiä. Analyysimenetelmistä kaikkein lupaavimpia testattiin työn kokeellisessa osassa. Diplomityön kokeellisessa osassa keskityttiin kehittämään muokatulle sellulle kvantitatiivista menetelmää DS:n määrittämiseksi Fourier-muunnos infrapuna-vaimennettu kokonaisheijastus (FTIR-ATR) spektrometrillä. Kirjallisuuskatsauksessa ei löytynyt yhtään dokumentoitua tutkimusta, jossa FTIR-ATR menetelmää olisi käytetty muokatun sellukuidun kvantitatiiviseen tutkimukseen. Muiden analyysimenetelmien, kuten alkuaineanalyysin, termogravimetrisen analyysin (TGA) ja valomikroskopian avulla pyrittiin tuottamaan lisätietoa muokkauksesta. Kvantitatiivisen FTIR-ATR menetelmän kehitykseen käytetyt muokatut sellukuidut olivat selluloosa-asetaattia ja selluloosa betainaattia. Saatujen tulosten perusteella muokattujen sulfiitti- ja kraft sellukuitujen DS:n kvantitatiivinen määrittäminen on mahdollista FTIR-ATR menetelmällä. Vähäinen kalibrointipisteiden määrä vaikeutti tarkan analyysimenetelmän tekemistä. Kehitetyn menetelmän suurimpina ongelmina olivat kiinteiden näytteiden heterogeenisyys sekä mahdollisten epäpuhtauksien tunnistaminen. Jatkotutkimusten avulla kehitettyä menetelmää on kuitenkin mahdollista käyttää muokattujen sellukuitujen jatkuvaan analysointiin selluteollisuudessa.

Production and Characterization of Endocylanase from Bacillus Pumilus Using Solidstate Fermentation and its Application in 'Paper Pulp Processing

In the present studies it is clear that Bacillus pumilus xylanase is having the characteristic suited for an industrial enzyme (xylanases that are active and stable at elevated temperatures and alkaline pH are needed). SSF production of xylanases and its application appears to be an innovative technology where the fermented substrate is the enzyme source that is used directly in the bleaching process without a prior downstream processing. The direct use of SSF enzymes in bleaching is a relatively new biobleaching approach. This can certainly benefit the bleaching process to lower the xylanase production costs and improve the economics and viability of the biobleaching technology. The application of enzymes to the bleaching process has been considered as an environmentally friendly approach that can reduce the negative impact on the environment exerted by the use of chlorine-based bleaching agents. It has been demonstrated that pretreatment of kraft pulp with xylanase prior to bleaching (biobleaching) can facilitate subsequent removal of lignin by bleaching chemicals, thereby, reducing the demand for elemental chlorine or improving final paper brightness. Using this xylanase pre-treatment, has resulted in an increased of brightness (8.5 Unit) when compared to non-enzymatic treated bleached pulp prepared using identical conditions. Reduction of the consumption of active chlorine can be achieved which results in a decrease in the toxicity, colour, chloride and absorbable organic halogen (AOX) levels of bleaching effluents. The xylanase treatment improves drainage, strength properties and the fragility of pulps, and also increases the brightness of pulps. This positive result shows that enzyme pre-treatment facilitates the removal of chromophore fragments of pulp there by making the process more environment friendly

Surface properties of eucalyptus pulp fibres as reinforcement of cement-based composites

The objective of the present work is to evaluate the effects of the surface properties of unrefined eucalyptus pulp fibres concerning their performance in cement-based composites. The influence of the fibre surface on the microstructure of fibre-cement composites was evaluated after accelerated ageing cycles, which simulate natural weathering. The surface of unbleached pulp is a thin layer that is rich in cellulose, lignin, hemicelluloses, and extractives. Such a layer acts as a physical and chemical barrier to the penetration of low molecular components of cement. The unbleached fibres are less hydrophilic than the bleached ones. Bleaching removes the amorphous lignin and extractives from the surface and renders it more permeable to liquids. Atomic force microscopy (AFM) helps in understanding the fibre-cement interface. Bleaching improved the fibre- cement interfacial bonding, whereas fibres in the unbleached pulp were less susceptible to the re-precipitation of cement hydration products into the fibre cavities (lumens). Therefore, unbleached fibres can improve the long-term performance of the fibre-cement composite owing to their delayed mineralization.

Hydrogen peroxide and supercritical carbon dioxide: a new bleaching stage for Eucalyptus kraft-O(2) pulps

Kraft pulp is currently bleached largely by the elemental chlorine free (ECF) technology with oxygen, chlorine dioxide, and hydrogen as active agents. This technology brought about significant environmental improvements in relation to standard processes based on chlorine gas and hypochlorite, but there is still need for further improvements. This study presents a novel environmentally friendly bleaching stage - the so-called `hydrogen peroxide in supercritical carbon dioxide`, P((SC-CO2)) - that can be adapted to current ECF bleaching processes, with preference in cases where hydrogen peroxide is already used. In this study, the P((SC-CO2)) stage was evaluated as a replacement to the last peroxide stage of the D(EP)DP bleaching sequence and to the first peroxide stage of the D(EP)DP sequence, for an oxygen delignified eucalypt kraft-O(2) pulp. The P((SC-CO2)) stage was run with 0.5% hydrogen peroxide, at 15% consistency, 70 degrees C, and 73 bar. The reaction time was 30 min. The performances of regular P stages and the new P((SC-CO2)) stage were compared. Promising results were observed with the DEP((SC-CO2))DP sequence; the P((SC-CO2)) decreased kappa number from 2.7 to 2.1, and the hexenuronic acid groups from 17.0 to 12.4 mmol kg(-1). The P((SC-CO2)) stage showed poor performance when applied in the D(EP)DP((SC-CO2)) sequence. It is concluded that the process presents potential but requires further optimization to improve selectivity and efficiency.

Geração de finos no branqueamento de pasta kraft de eucalipto e seu efeito nas propriedades do papel

Este trabalho teve por objetivo avaliar a quantidade de finos gerada por diferentes reagentes de branqueamento e seu efeito nas propriedades físicas e mecânicas da celulose kraft de eucalipto. A polpa foi branqueada por quatro sequências diferentes. Parte das amostras foi classificada em equipamento Bauer-McNett, sendo a parte não classificada (global) refinada para 40 ºSR, em moinho laboratorial PFI. As duas maiores porções de cada amostra proveniente da classificação foram também refinadas com o mesmo número de revoluções que a sua amostra global. Realizaram-se ensaios físicos e mecânicos das amostras refinadas, e suas fibras foram analisadas em equipamento FQA (Fiber Quality Analyser), antes e depois do refino. A maior quantidade de finos foi observada nas polpas refinadas e na sequência-referência. Os resultados de tração foram mais elevados e significativos nas amostras globais; as polpas classificadas não apresentaram diferença entre si, sendo atribuída a maior resistência à tração na presença de finos. A resistência ao rasgo foi afetada pelo comprimento das fibras e não pelo teor de finos. Os maiores valores de ascensão capilar Klemm ocorreram nas amostras classificadas em razão da ausência de finos e do maior comprimento de fibras.

Influência do cancro basal em Eucalyptus grandis nas propriedades da madeira e polpação kraft

The objective of this research is to assess the influences of basal canker on wood properties for the kraft pulp production. The material consisted of seeded E. grandis trees classified into 4 levels of basal canker severity (0, 1, 2 and 3) and installed in three soil types classified by texture (AQ1 and AQ2 - 10 to 15% clay, and LEm2 - 26 to 35 clay). The sampling consisted of randomly selecting five trees for each for each canker severity level and soil type, totaling 60 trees (4 canker levels x 3 soil types x 5 trees). These trees were fallen and cut into sections at 0, 25, 50, 75 and 100% of the commercial height for the collection of disk and logs of wood. The results showed that the soil texture influences in the Eucalyptus canker severity and this fact should be considered when assessing the wood properties and their final destination. The texture of the soil and the severe levels of basal canker influence the wood properties, and therefore the kraft pulping.

Xylanase and β-Xylosidase from Penicillium janczewskii: Production, Physico-Chemical properties, and application of the crude extract to pulp biobleaching

Extracellular xylanase and β-xylosidase production by a Penicillium janczewskii strain were investigated in liquid cultures with xylan from oat spelts under different physical and chemical conditions. The selected conditions for optimized production of xylanase and β-xylosidase were 7 days, pH 6.5, at 30 °C and 8 days, pH 5.0, at 25 °C, respectively. The xylanase exhibited optimal activity in pH 5.0 at 50 °C and the β- xylosidase in pH 4.0 at 75 °C. The xylanase was more stable at pH 6.0 to 9.5, while the β-xylosidase remained stable at pH ranging from 1.6 to 5.5. The xylanase half-life (T50) at 40, 50, and 60 °C was 183, 15, and 3 min, respectively. β-xylosidase half-life was 144, 8, and 4 min at 50, 65, and 75 °C, respectively. When applied to the biobleaching of Eucalyptus kraft pulp, xylanase dosages of 2 and 4 U/g dried pulp reduced, respectively, kappa number by 3.0 and 3.3 units after 1 h treatment, demonstrating that the use of P. janczewskii xylanases in this process is quite promising. The pulp viscosity was not altered, confirming the absence of cellulolytic enzymes in the fungal extract.

Dimensões de cavacos industriais de eucalipto e relações com polpação, resistência e morfologia de fibras na polpa

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Xylanase and beta-Xylosidase from Penicillium janczewskii: Production, Physico-chemical Properties, and Application of the Crude Extract to Pulp Biobleaching

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Quality of wood and pulp from a clone of Eucalyptus grandis planted at three locations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Modificação da pasta kraft de eucalipto para novas aplicações

Este trabalho constou num estudo da modificação da pasta kraft de eucalipto, utilizando uma técnica de processamento por alta pressão hidrostática com o intuito de melhorar a sua performance para novas aplicações tal como o papel tissue ou o papel para embalagens. Para tal pretendia-se melhorar algumas propriedades da pasta com a utilização da técnica de alta pressão hidrostática. Realizou-se um estudo preliminar onde se submeteu uma pasta branqueada A, não refinada, a um tratamento hiperbárico (TH) numa gama de pressões de 5000-8000 bar. Para uma pressão de 6000 bar constatou-se uma melhoria de cerca de 16 % no alongamento percentual na rotura, 17 % na resistência à tração, 27 % no índice de rebentamento e cerca de 19 % no índice de rasgamento. Posteriormente, e tendo em conta os resultados positivos verificados na pasta A, estudou-se o efeito do TH numa pasta branqueada B variando a consistência de tratamento (1,5% ou 3%) e o tempo de processamento (5 ou 10 minutos). Foi estudado também o efeito do TH quando aplicado antes e após a refinação da pasta. A pasta branca foi submetida à refinação num moinho PFI entre 1000 e 3000 rotações. Os resultados obtidos mostram que o TH realizado a menores consistências apresenta um efeito mais significativo nas propriedades físico-mecânicas de pastas e que o efeito é distinto quando o processamento é aplicado antes e depois da refinação, tendo-se registado melhoramentos das propriedades mecânicas apenas quando o TH ocorre após a refinação. A pasta kraft foi também modificada com anidrido alquenil succínico (ASA). A modificação da pasta de celulose com ASA resultou numa diminuição das propriedades mecânicas e para além disso não gerou qualquer alteração na termoplasticidade do material, no entanto registou-se um aumento na resistência à molhabilidade. Concluiu-se que o TH conduz a alterações ao nível de propriedades mecânicas e estruturais da pasta de interesse para a aplicação em papéis tissue no caso da pasta B. Para além disso a modificação da pasta com ASA resultou em alterações de interesse particular para papéis de embalagem.

TOXICITY EVALUATION AS A TOOL TO ASSES THE PERFORMANCE OF AN ANAEROBIC IMMOBILIZED BIOMASS REACTOR

Effluents from pulp mill are usually toxic and mutagenic. This characteristic is mainly a consequence of xenobiotic compounds that are formed during the process. Global parameters such as chemical oxidation demand, total organic carbon and others, do not permit identify whether the toxic potential was remedied by the treatments or not. The objective of this research was to evaluate the performance of an horizontal-flow anaerobic immobilized biomass reactor (HAIB) treating the bleaching effluent from a Kraft pulp mill using toxicological (Daphnia similis - Ceriodaphnia sdvestrii) mutagenicity and citotoxicological assays (Allium cepa L). The results showed high sensibility of the test-organisms and capability of the anaerobic reactor to remove compounds that are exerting toxic and mutagenic effects. The bioassays represented an attractive alternative to water quality analyzes and the performance evaluation of treatments.

Biodegradability and toxicity assessment of bleach plant effluents treated anaerobically

As part of an experimental project on the treatment of bleach plant effluents the results of biodegradability and toxicity assessment of effluents from a bench-scale horizontal anaerobic immobilized bioreactor (HAIB) are discussed in this paper. The biodegradability of the bleach plant effluents from a Kraft pulp mill treated in the HAIB was evaluated using the modified Zahn-Wellens test. The inoculum came from a pulp mill wastewater treatment plant and the dissolved organic carbon (DOC) was used as the indicator of organic matter removal. The acute and chronic toxicity removal during the anaerobic treatment was estimated using Daphnia similis and Ceriodaphnia silvestrii respectively. Moreover, the evaluation of chromosome aberrations (CA), micronucleus frequencies (MN) and mitotic index (IM) in Allium cepa cells were used as genotoxicity indicators. The results indicate that the effluents from the anaerobic reactor are amenable to aerobic polishing. Acute and chronic toxicity were reduced by 90 and 81%, respectively. The largest CA and MN incidence in the meristematic cells of A. cepa were observed after exposure to the raw bleach plant effluent. The HAIB was able to reduce the acute and chronic toxicity as well as chromosome aberrations and the occurrence of micronucleus.

Blocked diisocyanates as reactive coupling agents: Application to pine fiber-polypropylene composites

In this paper, composites from polypropylene and Kraft pulp (from Pinus radiata) were prepared. Phenyl isocyanate, unblocked and phenol blocked derivatives of 4,4`-methylenebis (phenyl isocyanate) (MDI) were used as coupling agents and the mechanical properties of the obtained composites analyzed. The results showed that the addition of such compatibilizers readily improved the tensile and flexural strengths of the composites. However, no significant variation in the mechanical properties was observed for composite formulations comprising different isocyanate compounds. Accordingly, the chemical structure of isocyanate derivatives did not affect extensively the mechanical properties of MDI-coupled pine fiber reinforced composites. These results were similar to those obtained in previous studies regarding the efficiency of organosilane coupling agents. In comparison to monoreactive isocyanates, the addition of MIDI increased considerably the mechanical properties of pine fiber-polypropylene composites. The mechanical anchoring of polymeric PP chains onto the irregular reinforcement surface supported this result. Non-isothermal DSC analysis showed a slowing effect of MDI on the crystallization kinetics of the coupled composites. This may have been the result of diminished polymer chain mobility in the matrix due to mechanical anchoring onto the fiber surface. Considering these results, the occurrence of strong bonds between the composite components was stated, rather than the unique existence of Van der Waals interactions among the non-polar structures. (c) 2008 Elsevier Ltd. All rights reserved.

Hybrid Reinforcement of Sisal and Polypropylene Fibers in Cement-Based Composites

Several studies using vegetable fibers as the exclusive reinforcement in fiber-cement composites have shown acceptable mechanical performance at the first ages. However, after the exposure to accelerated aging tests, these composites have shown significant reduction in the toughness or increase in embrittlement. This was mainly attributed to the improved fiber-matrix adhesion and fiber mineralization after aging process. The objective of the present research was to evaluate composites produced by the slurry dewatering technique followed by pressing and air curing, reinforced with combinations of polypropylene fibers and sisal kraft pulp at different pulp freeness. The physical properties, mechanical performance, and microstructural characteristics of the composites were evaluated before and after accelerated and natural aging. Results showed the great contribution of pulp refinement on the improvement of the mechanical strength in the composites. Higher intensities of refinement resulted in higher modulus of rupture for the composites with hybrid reinforcement after accelerated and natural aging. The more compact microstructure was due to the improved packing of the mineral particles with refined sisal pulp. The toughness of the composites after aging was maintained in relation to the composites at 28 days of cure.