A case study on the treatment and recycling of the effluent generated from a thermo-mechanical pulp mill in Brazil after the installation of a new bleaching process.

A Brazilian thermo-mechanical pulp mill (TMP) was evaluating the installation of a proposed bleaching process, with changes in the qualitative and quantitative characteristics of the wastewaters and the Effluent Treatment Plant (ETP). The objectives of this research were to evaluate the treatment plant configuration for the future industrial effluent, consisting of a flotation unit followed by an upflow anaerobic sludge blanket reactor (UASB), an activated sludge process and nanofiltration (NF) using polymeric membranes, and to study the technical feasibility of recycling the treated effluents in the industrial process. The possible options for recycling the treated effluent were determined through a water balance of the mill. The pulp quality was evaluated in laboratory bleaching assays, based on brightness and brightness reversion tests after the recycling of 50%, 75% and 100% of the treated effluent. The buildup of the non-process elements (NPE) in the industrial water cycle after each effluent recycling proportion was evaluated through computer simulation, using the Aspen Plus® simulator software. The future mill effluent, considering the implementation of a proposed bleaching stage with hydrogen peroxide, was generated in the laboratory and treated in a bench-scale effluent plant, simulating the future configuration. The treatment plant removed 99.8%, 99.2% and 61.6% of soluble COD, BOD5 and color, respectively. The water consumption was highest in the bleaching plant and, therefore, the recycling of 50%, 75% and 100% of the treated effluent for washing the pulp was simulated. The brightness and brightness reversion of the pulp, with 100% of the treated effluent used in the bleaching process, were similar to those provided by fresh water. The recycling of 100% of the treated effluent in the proposed treatment plant was possible in the TMP pulp mill without decreasing the pulp quality.

Isolation and characterization of acetylated glucuronoarabinoxylan from sugarcane bagasse and straw.

Sugarcane bagasse and straw are generated in large volumes as by-products of agro-industrial production. They are an emerging valuable resource for the generation of hemicellulose-based materials and products, since they contain significant quantities of xylans (often twice as much as in hardwoods). Heteroxylans (yields of ca 20% based on xylose content in sugarcane bagasse and straw) were successfully isolated and purified using mild delignification followed by dimethyl sulfoxide (DMSO) extraction. Delignification with peracetic acid (PAA) was more efficient than traditional sodium chlorite (NaClO2) delignification for xylan extraction from both biomasses, resulting in higher extraction yields and purity. We have shown that the heteroxylans isolated from sugarcane bagasse and straw are acetylated glucuronoarabinoxylans (GAX), with distinct molecular structures. Bagasse GAX had a slightly lower glycosyl substitution molar ratio of Araf to Xylp to (0.5:10) and (4-O-Me)GlpA to Xylp (0.1:10) than GAX from straw (0.8:10 and 0.1:10 respectively), but a higher degree of acetylation (0.33 and 0.10, respectively). A higher frequency of acetyl groups substitution at position α-(1→3) (Xyl-3Ac) than at position α-(1→2) (Xyl-2Ac) was confirmed for both bagasse and straw GAX, with a minor ratio of diacetylation (Xyl-2,3Ac). The size and molecular weight distributions for the acetylated GAX extracted from the sugarcane bagasse and straw were analyzed using multiple-detection size-exclusion chromatography (SEC-DRI-MALLS). Light scattering data provided absolute molar mass values for acetylated GAX with higher average values than did standard calibration. Moreover, the data highlighted differences in the molar mass distributions between the two isolation methods for both types of sugarcane GAX, which can be correlated with the different Araf and acetyl substitution patterns. We have developed an empirical model for the molecular structure of acetylated GAX extracted from sugarcane bagasse and straw with PAA/DMSO through the integration of results obtained from glycosidic linkage analysis, 1H NMR spectroscopy and acetyl quantification. This knowledge of the structure of xylans in sugarcane bagasse and straw will provide a better understanding of the isolation-structure-properties relationship of these biopolymers and, ultimately, create new possibilities for the use of sugarcane xylan in high-value applications, such as biochemicals and bio-based materials.

Cellulose pulp produced from bulrush fiber / Produção de polpa celulósica a partir das fibras de junco

ABSTRACT: Brazil continues to use wood as the principal raw material source for the pulp industry; although, non-wood fibers have been revealed to be a competent substitute to produce paper with different and exceptional properties. Keeping this in focus, this study aimed to assess potential of Schoenoplectus californicus fibers (C. A. Mey.) Soják, commonly identified as bulrush or reed, in cellulosic pulp generation, as an alternative fiber source for the pulp and paper industry. On analyzing the chemical composition of reed fibers, extractives of lignin, carbohydrates, uronic acids and minerals were reported. Physico-chemical characteristics of reed-based cellulosic pulp were estimated including viscosity, hexenuronic acids, etc., as well as anatomical features of length, width, etc. From the chemical analyses of the reed the presence of high concentrations of extractives and silica was clear, making them unfit as raw material for cellulosic pulp production. Pulp kraft pulping process produced brown pulps low in viscosity (34.5m Pa.s) and hexenuronic acid content. Reed is thus classifiable as short-fiber source for pulp and paper industries.

RESUMO: A madeira é a principal fonte de matéria prima utilizada nas indústrias de celulose no Brasil, porém o emprego de fibras não madeireiras pode ser uma alternativa satisfatória para a fabricação de papéis com propriedades diferenciadas e especiais. Nesse sentido, o objetivo desse trabalho foi avaliar o potencial das fibras de Schoenoplectus californicus (C.A. Mey.) Soják, popularmente conhecido como junco, na produção de polpa celulósica, como fonte alternativa de fibras para as indústrias do setor de celulose e papel. Nas fibras do junco foram realizadas análises de composição química, entre elas: teores de extrativos, lignina, carboidratos, ácidos urônicos e minerais. As polpas celulósicas produzidas a partir do junco foram avaliadas no que diz respeito às características físico-químicas (viscosidade, ácidos hexenurônicos, etc.) e anatômicas (comprimento, largura, etc.). As análises químicas demonstraram que as fibras do junco apresentam altos teores de extrativos e sílica, o que as tornam uma matéria prima desfavorável para a produção de polpa celulósica. O processo de polpação kraft do junco resultou em polpas marrons de baixa viscosidade (34,5m Pa.s) e com baixos teores de ácidos hexenurônicos. O junco pode ser classificado como fonte de fibras curtas para as indústrias de celulose e papel.

As xilanas nas propriedades de polpas marrons de eucalipto / Xylans on eucalyptus brown pulp propertie

O objetivo deste estudo foi avaliar as propriedades de polpas kraft marrons de madeiras de Eucalyptus grandise Eucalyptus urograndisde composição química distinta, principalmente em relação aos seus conteúdos de xilanas, para fabricação de papéis. As polpas marrons de número kappa 17-18 e conteúdos de xilanas variando de 6 a 21% foram produzidas sob diferentes protocolos de cozimento: 1) kraft convencional; 2) pré-hidrólise kraft; 3) kraft de alta alcalinidade; e 4) kraft de alto rendimento. As polpas marrons foram refinadas em moinho PFI e seus respectivos papéis produzidos foram avaliados quanto às suas propriedades físico-mecânicas e ópticas. De modo geral, as propriedades de resistência dos papéis foram beneficiadas pelo conteúdo de xilanas. Para níveis muito altos de refino, ocorreram quedas bruscas de resistência ao rasgo para os papéis e o consumo de energia de refino foi influenciado pelo conteúdo de xilanas nas polpas marrons. Os mais altos valores de volume específico aparente foram obtidos para os papéis com baixo conteúdo de xilanas, o que os torna interessantes, se branqueados, no segmento de papéis tissue. Os papéis com elevado conteúdo de xilanas apresentaram-se economicamente atrativos e com características de resistências adequadas para o segmento de papéis de imprimir e escrever.

The objective of this study was to evaluate properties of brown pulp from Eucalyptus grandisand Eucalyptus urograndisof distinct chemical composition, mainly in refers to its xylans content, for the manufacture of tissue and printing and writing (P&W) paper grades. Brow pulps of kappa number 17-18 and xylans contents varying 6-21% had been produced under different cooking protocols: 1) conventional kraft; 2) pre-hydrolysis kraft; 3) high alkalinity kraft; and 4) kraft of high yield. The brown pulps had been beated in PFI mill and its respective produced papers had been evaluated as regards physical-mechanical and optic properties. The highest bulk values had been gotten for papers with low xylans contents, what had revealed interesting, if bleached, in the manufacture of tissue papers. The papers with high xylans contents, had been presented technically viable and with resistance characteristics adjusted for the manufacture of P&W papers.

Production of fermentable sugars from sugarcane bagasse by enzymatic hydrolysis after autohydrolysis and mechanical refining.

The autohydrolysis process has been considered a simple, low-cost and environmental friendly technology for generation of sugars from biomass. In order to improve accessibility of enzymes during enzymatic hydrolysis as well as to allow the recovery of hemicellulose in the filtrate, the sugarcane bagasse was pretreated using autohydrolysis followed by a mechanical refining process. The autohydrolysis was carried out in three different conditions. Autohydrolysis at 190°C for 10min provided the highest overall sugar (19.2/100g raw bagasse) in prehydrolyzate. The enzymatic hydrolysis step was performed for all the post-treated solids with and without refining at enzyme loadings of 5 and 10FPU/g for 96h. A total of 84.4% of sugar can be recovered from sugarcane bagasse at 180°C for 20min with 5 FPU/g enzyme charge. The economic analysis for the proposed method showed that the bioethanol production can have a financial return larger than 12%.

Chrysoporthe cubensis: a new source of cellulases and hemicellulases to application in biomass saccharification processes.

The plant pathogenic fungus Chrysoporthe cubensis was cultivated under solid state employing different substrates and the highest endoglucanase (33.84Ug(-1)), FPase (2.52Ug(-1)), ß-glucosidase (21.55Ug(-1)) and xylanase (362.38Ug(-1)) activities were obtained using wheat bran as carbon source. Cellulases and xylanase produced by C. cubensis showed maximal hydrolysis rate at pH 4.0 and in a temperature range of 50-60°C. All enzymatic activities were highly stable at 40 and 50°C through 48h of pre-incubation. Saccharification of alkaline pretreated sugarcane bagasse by crude enzyme extract from C. cubensis resulted in release of 320.8mg/g and 288.7mg/g of glucose and xylose, respectively. On another hand, a similar assay employing commercial cellulase preparation resulted in release of 250.6mg/g and 62.1mg/g of glucose and xylose, respectively. Cellulolytic extract from C. cubensis showed a great potential to be used in biomass saccharification processes.

Characterization of cellulolytic extract from Pycnoporus sanguineus PF-2 and its application in biomass saccharification.

The aim of this work was to evaluate the biochemical features of the white-rot fungi Pycnoporus sanguineus cellulolytic complex and its utilization to sugarcane bagasse hydrolysis. When cultivated under submerged fermentation using corn cobs as carbon source, P. sanguineus produced high FPase, endoglucanase, ß-glucosidase, xylanase, mannanase, α-galactosidase, α-arabinofuranosidase, and polygalacturonase activities. Cellulase activities were characterized in relation to pH and temperature. ß-Glucosidase and FPase activities were higher at 55 °C, pH 4.5, and endoglucanase activity was higher at 60 °C, in a pH range of 3.5-4.0. All cellulase activities were highly stable at 40 and 50 °C through 48 h of pre-incubation. Crude enzymatic extract from P. sanguineus was applied in a saccharification experiment using acid-treated and alkali-treated sugarcane bagasse as substrate, and the hydrolysis yields were compared to that obtained by a commercial cellulase preparation. Reducing sugar yields of 60.4% and 64.0% were reached when alkali-treated bagasse was hydrolyzed by P. sanguineus extract and commercial cellulase, respectively. Considering the glucose production, it was observed that P. sanguineus extract and commercial cellulase ensured yields of 22.6% and 36.5%, respectively. The saccharification of acid-treated bagasse was lower than that of alkali-treated bagasse regardless of the cellulolytic extract. The present work showed that P. sanguineus has a great potential as an enzyme producer for biomass saccharification.

Thermal and spectroscopic analyses on the molecular interaction between eucalyptus kraft pulp components and offset printing inks

Thermal and infrared spectroscopic analyzes were carried out in order to study the kind of interaction between the anatomical components of the bleached eucalyptus kraft pulp with offset inks. A Bauer-McNett fiber classifier was used in order to obtain the anatomical components of the pulp, separately. The determinations of the enthalpy of the processes occurring in the samples of inks and pulp, as well as the enthalpy of these components interactions were obtained by Differential Scanning Calorimetry. In the interaction between pulp and offset ink, the reduced enthalpy values of the endothermic peak were interpreted as due to the released energy for adhesion of the ink pigment to the substratum. The low enthalpy value, 58 to 121 cal.g -, ¹indicated that the settling of the ink occurs by physical interactions. The pulp fraction enriched with vessel elements caused a higher energy release during the adherence of the pigment into the pulp.

O conhecimento técnico-científico das interações que ocorrem no processo de impressão offset é escasso, embora várias observações mostrem sua importância. O objetivo deste trabalho foi estudar por análises térmicas e espectroscópicas, na região 1do infravermelho, o tipo de interação dos componentes anatômicos da polpa branqueada kraft de eucalipto com tintas de impressão offset. Foi utilizado um classificador de fibras Bauer-McNett com o intuito de se obter os componentes anatômicos da polpa separadamente. As determinações da entalpia dos processos que ocorrem com as amostras de tintas, polpa e também a entalpia de interação destes componentes foram obtidas por Calorimetria Diferencial de Varredura. Na interação entre polpa e tinta offset, a redução dos valores de entalpia do pico endotérmico foi interpretada como sendo devida à liberação de energia para a adesão do pigmento da tinta ao substrato. Os baixos valores de entalpia (58 a 121 cal.g-1) indicam que o assentamento da tinta ocorre por meio de interações físicas A fração de polpa enriquecida com elementos de vasos acarreta uma maior liberação de energia, durante a aderência do pigmento na polpa.