Estudos da polpação kraft, branqueamento e refino de eucalyptus grandis x eucalyptus urophylla

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Wood and fiber properties of Norway spruce and its suitability for thermomechanical pulping.

In the first part of the study, the selected wood and fiber properties were investigated in terms of their occurrence and variation in wood, as well as their relevance from the perspective of thermomechanical pulping process and related end-products. It was concluded that the most important factors were the fiber dimensions, juvenile wood content, and in some cases, the content of heartwood being associated with extremely dry wood with low permeability in spruce. With respect to the above properties, the following three pulpwood assortments of which pulping potential was assumed to vary were formed: wood from regeneration cuttings, first-thinnings wood, and sawmill chips. In the experimental part of the study the average wood and fiber characteristics and their variation were determined for each raw material group prior to pulping. Subsequently, each assortment - equaling about 1500 m3 roundwood - was pulped separately for a 24 h period, at constant process conditions. The properties of obtained newsgrade thermomechanical pulps were then determined. Thermomechanical pulping (TMP) from sawmill chips had the highest proportion of long fibers, smallest proportion of fines, and had generally the coarsest and longest fibers. TMP from first-thinnings wood was just the opposite, whereas that from regeneration cuttings fell in between the above two extremes. High proportion of dry heartwood in wood originating from regeneration cuttings produced a slightly elevated shives content. However, no differences were found in pulp specific energy consumption. The obtained pulp tear index was clearly best in TMP made from sawmill chips and poorest in pulp from first-thinnings wood, which had generally inferior strength properties. No dramatical differences in any of the strength properties were found between pulp from sawmill residual wood and regeneration cuttings. Pulp optical properties were superior in TMP from first-thinnings. Unexpectedly, no noticeable differences, which could be explained with fiber morphology, were found in sheet density, bulk, air permeance or roughness between the three pulps. The most important wood quality factors in this study were the fiber length, fiber cross-sectional dimensions and percentage juvenile wood. Differences found in the quality of TMP manufactured from the above spruce assortments suggest that they could be segregated and pulped separately to obtain specific product characteristics, i.e., for instance tailor-made end-products, and to minimize unnecessary variation in the raw material quality, and hence, pulp quality.

The initial phase of sodium sulfite pulping of softwood : A comparison of different pulping options

Single stage and two-stage sodium sulfite cooking were carried out on either spruce, pine or pure pine heartwood chips to investigate the influence of several process parameters on the initial phase of such a cook down to about 60 % pulp yield. The cooking experiments were carried out in the laboratory with either a lab-prepared or a mill-prepared cooking acid and the temperature and time were varied. The influences of dissolved organic and inorganic components in the cooking liquor on the final pulp composition and on the extent of side reactions were investigated. Kinetic equations were developed and the activation energies for delignification and carbohydrate dissolution were calculated using the Arrhenius equation. A better understanding of the delignification mechanisms during bisulfite and acid sulfite cooking was obtained by analyzing the lignin carbohydrate complexes (LCC) present in the pulp when different cooking conditions were used. It was found that using a mill-prepared cooking acid beneficial effect with respect to side reactions, extractives removal and higher stability in pH during the cook were observed compared to a lab-prepared cooking acid. However, no significant difference in degrees of delignification or carbohydrate degradation was seen.  The cellulose yield was not affected in the initial phase of the cook however; temperature had an influence on the rates of both delignification and hemicellulose removal. It was also found that the  corresponding activation energies increased in the order:  xylan, glucomannan, lignin and cellulose. The cooking temperature could thus be used to control the cook to a given carbohydrate composition in the final pulp. Lignin condensation reactions were observed during acid sulfite cooking, especially at higher temperatures. The LCC studies indicated the existence of covalent bonds between lignin and hemicellulose components with respect to xylan and glucomannan. LCC in native wood showed the presence of phenyl glycosides, ϒ-esters and α-ethers; whereas the α-ethers  were affected during sulfite pulping. The existence of covalent bonds between lignin and wood polysaccharides might be the rate-limiting factor in sulfite pulping.

Fraccionamiento del licor gastado en pasteado al sulfito ácido mediante ultrafiltración

Lignosulphonates (LS) and fermentable sugars are the main components of spent sulphite liquors (SSL) produced in acid sulphite pulping. In spite of different methods have been used for spent liquor fractionation such as precipitation or vaporization; membrane technology allows the separation of these components from the SSL due to their different size molecular weight, offering great advantages with regards to the traditionally methods (less energy consumption, high selective separation, and many others). In the present study, ceramic membranes with different cut-offs (15 kDa, 5 kDa and 1 kDa) were used to achieve the sugar purification and the LS concentration. The membranes were evaluated according to their efficacy and efficiency properties. Different series system were tested in order to improve the aptitudes of a singular membrane. The system with the three membranes in series (15, 5 and 1 kDa respectively) obtained the most purified permeate stream, referred to the sugar content. Also, a characterisation of the LS contained in the different streams produced in this system was carried out in order to know in a more precise manner the valorisation potential of these components by means of biorefinery processes.

Walker Brothers Quarries Limited fonds, 1975, 1980-1981, 1984, 1987-1989

Serving the Niagara and surrounding areas for over 120 years, Walker Industries has made its impact not only commercially, but also culturally. Beginning in 1875 with the erection of a stone sawing mill on a property John Walker purchased from the Welland Canal Loan Company. One of the first projects Walker cut stone for was the Merritton Town Hall. In 1882 the business expanded to include Walkers children, changing the name to Walker & Sons. Eventually in 1887 the two eldest sons took control of the business operation and their partnership changed the company’s name to Walker Brothers, the same year the company began operating its first quarry. The quarry was conveniently located alongside the 3rd Welland canal, offering easy access to Toronto and Hamilton. It was also close to the railway system which allowed immediate access to Thorold and Niagara Falls and later access to parts of Ontario and Quebec. The quarry supplied stone to build numerous halls and armouries across Ontario. A use was also found for the ‘waste products’ of cutting the limestone. Leftover stone chips were sent to paper mills, where stone was needed as part of the sulphite pulp process for making paper. Beginning to supply the Ontario Paper Company with stone in 1913, meant not only long, hard, work, but also more profit for the company. Before mechanization, most of the loading and unloading of the stone was done by hand, taking 19 man-hours to load an 18 yard railway car. Mechanization followed in 1947 when the plant became fully mechanized making the work easier and increasing production rates. In 1957 the company moved from its original location and opened the St. Catharines Crushed Stone Plant.

Modification of hemicellulose content by antisense down-regulation of UDP-glucuronate decarboxylase in tobacco and its consequences for cellulose extractability

Extractability and recovery of cellulose from cell walls influences many industrial processes and also the utilisation of biomass for energy purposes. The utility of genetic manipulation of lignin has proven potential for optimising such processes and is also advantageous for the environment. Hemicelluloses, particularly secondary wall xylans, also influence the extractability of cellulose. UDP-glucuronate decarboxylase produces UDP-xylose, the precursor for xylans and the effect of its down-regulation on cell wall structure and cellulose extractability in transgenic tobacco has been investigated. Since there are a number of potential UDP-glucuronate decarboxylase genes, a 490 bp sequence of high similarity between members of the family, was chosen for general alteration of the expression of the gene family. Sense and antisense transgenic lines were analysed for enzyme activity using a modified and optimised electrophoretic assay, for enzyme levels by western blotting and for secondary cell wall composition. Some of the down-regulated antisense plants showed high glucose to xylose ratios in xylem walls due to less xylose-containing polymers, while arabinose and uronic acid contents, which could also have been affected by any change in UDP-xylose provision, were unchanged. The overall morphology and stem lignin content of the modified lines remained little changed compared with wild-type. However, there were some changes in vascular organisation and reduction of xylans in the secondary walls was confirmed by immunocytochemistry. Pulping analysis showed a decreased pulp yield and a higher Kappa number in some lines compared with controls, indicating that they were less delignified, although the level of residual alkali was reduced. Such traits probably indicate that lignin was less available for removal in a reduced background of xylans. However, the viscosity was higher in most antisense lines, meaning that the cellulose was less broken-down during the pulping process. This is one of the first studies of a directed manipulation of hemicellulose content on cellulose extractability and shows both positive and negative outcomes.

Modification of hemicellulose content by antisense down-regulation of UDP-glucuronate decarboxylase in tobacco and its conscequence for cellulose extractability

Extractability and recovery of cellulose from cell walls influences many industrial processes and also the utilisation of biomass for energy purposes. The utility of genetic manipulation of lignin has proven potential for optimising such processes and is also advantageous for the environment. Hemicelluloses, particularly secondary wall xylans, also influence the extractability of cellulose. UDP-glucuronate decarboxylase produces UDP-xylose, the precursor for xylans and the effect of its down-regulation on cell wall structure and cellulose extractability in transgenic tobacco has been investigated. Since there are a number of potential UDP-glucuronate decarboxylase genes, a 490 bp sequence of high similarity between members of the family, was chosen for general alteration of the expression of the gene family. Sense and antisense transgenic lines were analysed for enzyme activity using a modified and optimised electrophoretic assay, for enzyme levels by western blotting and for secondary cell wall composition. Some of the down-regulated antisense plants showed high glucose to xylose ratios in xylem walls due to less xylose-containing polymers, while arabinose and uronic acid contents, which could also have been affected by any change in UDP-xylose provision, were unchanged. The overall morphology and stem lignin content of the modified lines remained little changed compared with wild-type. However, there were some changes in vascular organisation and reduction of xylans in the secondary walls was confirmed by immunocytochemistry. Pulping analysis showed a decreased pulp yield and a higher Kappa number in some lines compared with controls, indicating that they were less delignified, although the level of residual alkali was reduced. Such traits probably indicate that lignin was less available for removal in a reduced background of xylans. However, the viscosity was higher in most antisense lines, meaning that the cellulose was less broken-down during the pulping process. This is one of the first studies of a directed manipulation of hemicellulose content on cellulose extractability and shows both positive and negative outcomes.

Monodisperse lignin fractions as standards in size-exclusion analysis Comparison with polystyrene standards

The difficulty of preparing monodisperse lignin fractions on a large scale is a limiting factor in many applications. The present paper addresses this problem by examining the properties and size-exclusion behavior of lignin isolated by the acetosolv pulping process from post-extraction crushed sugarcane bagasse. The isolated lignin was subjected to a solvent pretreatment, followed by preparative gel permeation chromatography fractionation. The fractions were analyzed by high-performance size-exclusion chromatography (HPSEC) and these samples showed a great decrease in polydispersity, compared to the original acetosolv lignin. Several fractions of very low polydispersity, close to unity, were employed as calibration curve standards in HPSEC analysis. This original analytical approach allowed calibration with these lignin fractions to be compared with the polystyrene standards that are universally employed for lignin molecular mass determination. This led to a noteworthy result, namely that the lignin fractions and polystyrene standards showed very similar behavior over a large range of molecular masses in a typical HPSEC analysis of acetosolv lignin. (C) 2009 Elsevier B.V. All rights reserved.

Surface esterification of cellulose fibres: Processing and characterisation of low-density polyethylene/cellulose fibres composites

Low-density polyethylene was filled with cellulose fibres from sugar cane bagasse obtained from organosolv/supercritical carbon dioxide pulping process. The fibres were also used after chemical modification with octadecanoyl and dodecanoyl chloride acids. The morphology, thermal properties, mechanical properties in both the linear and nonlinear range, and the water absorption behaviour of ensuing composites were tested. The evidence of occurrence of the chemical modification was checked by X-ray photoelectron spectrometry. The degree of polymerisation of the fibres and their intrinsic properties (zero tensile strength) were determined. It clearly appeared that the surface chemical modification of cellulose fibres resulted in improved interfacial adhesion with the matrix and higher dispersion level. However, composites did not show improved mechanical performances when compared to unmodified fibres. This surprising result was ascribed to the strong lowering of the degree of polymerisation of cellulose fibres (as confirmed by the drastic decrease of their zero tensile strength) after chemical treatment despite the mild conditions used. (c) 2007 Elsevier Ltd. All rights reserved.

Ultrathin films of lignins as a potential transducer in sensing applications involving heavy metal ions

Lignins extracted from sugar cane bagasse using different alcohols in the organosolv-CO(2) supercritical pulping process have been applied in the fabrication of ultrathin films through the Langmuir-Blodgett technique. Langmuir films were characterized by surface pressure versus mean molecular area (Pi-A) isotherms to exploit the sensitivity of nanostructured lignin films to metallic ions (Cu(2+), Cd(2+) and Pb(2+)). The Pi-A isotherms were shifted to larger molecular areas when heavy metal ions are present into the subphase, which might be related to electrostatic repulsions between metallic ions entrapped within the lignin molecular structure. Taking the advantage of metal incorporation, Langmuir monolayers were transferred onto solid substrates forming Langmuir-Blodgett (LB) films to be used as a transducer in an "electronic tongue" system to detect Cu(2+) in aqueous solution below threshold standard established by the Brazilian regulation. Both techniques impedance spectroscopy and electrochemistry have been used in these experiments. Complementary, Fourier transform infrared (FTIR) spectroscopy recorded for LB films before and after soaking into Cu(2+) aqueous solution revealed an interaction between the lignin phenyl groups and the metallic ion. (C) 2007 Elsevier B.V.. All rights reserved.

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Cinética da remoção dos extrativos da madeira de Eucalyptus grandis durante polpação Kraft

Kinetics of the removal of Eucalyptus grandis wood extractives during Kraft pulping. The objective of this work was to study the kinetics of the removal of Eucalyptus grandis wood extractives during Kraft pulping. The pulping was done in steel tubular reactors using wood saw under the following conditions: active alkali = 14%, sulfidity = 25%; liquor-to-wood ratio = 10 L kg(-1) of dry wood; and temperatures of 130, 150, 160 and 180 C during 30, 60, 90, 120, 150 and 180 minutes. After pulping, analyses were conducted of the yield and extractives in residue (pulp and reject). Total extractives (ethyl alcohol-toluene (1:2), ethyl alcohol and hot water, respectively) and soluble extractives in acetone were analyzed. The results showed that most extractives are degraded in the first 30 minutes of the pulping process. It was observed that the removal occurs in two different stages: the first is rapid, where the majority of the extractives are removed, and the last is slow, where few extractives are removed.

Modelo de otimização para seleção de árvores matrizes de Eucalyptus grandis

Individual data of basic density and volume of wood, pulp kappa number, soluble lignin, cost of pulping process as well as gravimetric gross yield of pulping process were used from 64 trees of Eucalyptus grandis W. Hill ex Maiden from a commercial population at Lençóis Paulista, SP. The Eucalyptus grandis's seeds were originally from a Seed Production Area (SPA) of Duratex S/A at Botucatu, SP. Obtained data were quantified considering objective of maximization no-bleaching pulp and volume and mass wood restriction, mass of residual and soluble lignin, planted area and pulping process cost. it has also been aimed a selection method for matrix trees through mathematical programming techniques. Obtained strategy maximized the economical result, selected matrix trees and followed all limits of technological and organizing productivities imposed by the company. It also aimed the production of no-bleaching pulp within the planned time.

Utilização de resíduos agronômicos da mandioca para fabricação de papéis especiais como recurso alternativo para a comunicação visual

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Some Physical and Mechanical Properties of Medium-Density Fiberboard Made from Giant Bamboo

The objective of this study was to evaluate the density, density profile, water swelling and absorption, modulus of elasticity and rupture from static bending, and tensile strength of experimental medium-density fiberboards manufactured using Dendrocalamus giganteus (Munro bamboo). The fiber production was carried out through the chemo-thermo-mechanical pulping process with four different conditions. The panels were made with 10% urea formaldehyde resin based on dry weight of the fibers, 2.5% of a catalyzer (ammonium sulfate) and 2% paraffin. The results indicate that treatments with the highest alkali (NaOH) percentage, time and splinter heating temperature improved the physical properties of the panels. The root-fiber interface was evaluated through scanning electron microscopy in fracture zones, which revealed fibers with thick, inflexible walls. The panels' mechanical properties were affected due to the fiber wall characteristics and interaction with resin. Giant bamboo fiber has potential for MDF production, but other studies should be carried out.