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- Effect of unbleached pulp kappa number on the kinetics of chlorine dioxide delignificationPublication . Simões, Rogério; Barroca, Maria J. M. C.; Castro, José Almiro A. M.Chlorine dioxide delignification of different unbleached kraft pulps from Eucalyptus globulus, having Kappa numbers of 12 to 18, was studied in the temperature range of 285 K to 358 K. The effect of the unbleached pulp Kappa number on the initial fast phase of delignification was investigated with respect to the depletion factors for Kappa number and chlorine dioxide concentration, as proposed by Barroca et al. Furthermore, the behaviour of the floor lignin content of the pulp, or the floor Kappa number, was analysed within this range. The results show that all pulps exhibit a similar pattern, with respect to temperature, in depletion factors for Kappa number and chlorine dioxide concentration. The degree of normalised delignification and chlorine dioxide consumption is very similar and independent of the Kappa number of the unbleached pulps. Moreover, the results reveal that there is a strong correlation between the floor lignin content and the temperature, and that this correlation is applicable to a wide range of unbleached pulp Kappa numbers, since the residual Kappa number is independent of its initial value. The results enable the general application of a kinetic model to kraft pulps with different unbleached Kappa numbers.
- Toxicity reduction and biodegradability enhancement of cork processing wastewaters by ozonationPublication . Gomes, A.C.; Silva, Lúcia; Simões, Rogério; Canto, N.; Albuquerque, AntonioBiodegradability enhancement and detoxification of cork boiling wastewater (CBW) are required for the successful implementation of biological treatment options. We studied the possibility of achieving these goals through ozonation pre-treatment by experimenting on the effect of ozone dose and pH. The CBW used had a pH of 5.81, a chemical oxygen demand (COD) of 1,865 mg L-1, a biochemical oxygen demand (BOD5) of 498 mg L-1 and total phenol (TP) and tannin compounds concentrations of 523 and 399 mg L-1, respectively. The ozone doses ranged from 0.27 to 2.63 for the O-3(applied)/COD0 ratios with samples at natural pH and set to 3.33 and 9.96. Ozonation allowed the BOD20/COD ratio (biodegradability index) to increase from 0.37 to 0.63 and a toxicity reduction from 3.08 to 1.24 TU (Microtox). The corresponding removals obtained were 15.2-62.0%, 38.4-83.2% and 56.7-92.1% for COD, TP and colour, respectively. The best outcome of ozonation pre-treatment requires O-3(applied)/COD0 ratios over 1.5 and an acid pH. The increase of TP removals with ozone dose at acid pH led to biodegradability enhancement and CBW detoxification. However, for similar conditions the highest COD removals were obtained at alkaline pH due to the hydroxyl radicals' high oxidation ability but lack of selectivity.
- Biodegradability enhancement and detoxification of cork processing wastewater molecular size fractions by ozonePublication . Santos, Diana C.; Silva, Lúcia; Albuquerque, Antonio; Simões, Rogério; Gomes, A.C.Cork boiling wastewater pollutants were fractionated by sequential use of four ultrafiltration membranes and five fractions were obtained: four retentates (>100, 50-100, 20-50 and 10-20 kDa) and one permeate (<10 kDa); which were used to study the correlation of molecular size with biodegradability and toxicity before and after ozonation. The results show that molecular size is correlated with organic load and restrains biodegradability. The fraction with >100 kDa corresponds to 56% of the organic load and the one with <10 kDa only 8%. The biodegradability of fractions increased 182% with fractions molecular size reduction from >100 to < 10 kDa and the chemical oxygen demand (COD) was from 3436 to 386 mg L-1. For biodegradability enhancement the best outcome of ozonation was obtained with compounds having molecular size >20 kDa and range from 5% up to 175% for applied ozone doses to COD ratios between 0.15 and 0.38.
- Acid sulfite pretreatment in the enzymatic hydrolysis of Cytisus striatus: optimization strategyPublication . Vaz, Álvaro; Gomes, Tânia; Simões, RogérioEthanol production from lignocellulosic material includes three major steps: biomass pretreatment, which fragments the lignocellulosic matrix to facilitate the enzymes access to the substrate; hydrolysis, where the polysaccharides are converted into fermentable sugars (e.g. glucose and xylose); and finally, fermentation that produces ethanol or other biologically based chemicals (e.g. lactic acid, succinic acid). The aim of the present work was to study the effect of some operative variables of the pretreatment stage, namely sodium hydrogen sulfite and sulfuric acid loadings, temperature and time, on the release of sugars in the enzymatic hydrolysis of Cytisus striatus, performed applying a Novozymes® cocktail, with fixed charges and operating conditions. Wood branches were chipped and submitted to different reaction conditions, with a central composite experimental design 2^4+star, exploring the following variables: sulfuric acid charge (0-3%, on wood), sodium bisulfite charge (0-4 %, on wood), maximum temperature (150-190ºC) and time at maximum temperature (0-30 minutes). After pretreatment, the acid hydrolysates were recovered, the solid residues were mechanically disintegrated and thereafter subjected to enzymatic hydrolysis with an enzymatic cocktail from Novozymes®. Sugars and by-products released in the sulphite pretreatment and enzymatic treatment hydrolysates were analyzed by HPLC.
- Effect of carry-over on the kinetics of chlorine dioxide delignification of an unbleached hardwood kraft pulpPublication . Simões, Rogério; Barroca, Maria J. M. C.; Castro, José Almiro A. M.This work is concerned with the kinetics of the prebleaching stage of a kraft pulp of Eucalyptus globulus with chlorine dioxide. Its main purpose is to discuss the influence of the degree of washing, expressed as the COD of the pulp, on the kinetics and stoichiometry of chlorine dioxide delignification. The effect of the carry-over on the rate of delignification of a Do stage was studied over time for pulps with different initial organic charges (COD). A set of experiments was specially designed to discriminate the individual role of lignin and of COD upon the initial consumption of chlorine dioxide. A modified mathematical model, taking into account the reactions of chlorine dioxide with both lignin and the carry-over, has been developed. In this model, the initial chlorine dioxide consumption (in the fast phase of reaction) is dependent on two factors: the carry-over of the pulp and the temperature of operation. However, the carry-over does not affect the corresponding initial depletion factor for the Kappa number. The role of the dissolved organic material, carried with the pulp, upon the rate of reaction in the slow period is better described in the stoichiometry. The fit of the experimental results obtained for pulps with different COD reveals good prediction capabilities for both Kappa number and chlorine dioxide concentration in a conventional D0 stage.
- Determination of sugar content in Pinus pinaster and its corresponding hollocellulose, cellulose and kraft pulpsPublication . Duarte, Ana Paula; Gaiolas, Carla Sofia Cardona Jorge; Belgacem, Mohamed Naceur; Simões, RogérioThis paper deals with the study of the polysaccharide complex from Portuguese Pinus pinaster, as well as from its main components, i.e., holocellulose, cellulose and pulps obtained using different cooking conditions. Nordic Pinus sylvestris was also studied in order to compare it with Portuguese pine. Two methods were used: one consisted of the hydrolysis of polysaccharides with trifluoroacetic acid (TFA) and quantification of the amount of each sugar using High Performance Liquid Chromatography (HPLC). The latter approach used here consisted of the hydrolysis of the samples under scrutiny by sulphuric acid and converting it into alditols, which were then esterified before injecting to Gas Chromatography coupled with Mass Spectrometry. Myo-inositol was used as an internal standard. The results obtained by the two methods showed that the TFA procedure prevents monosaccharide degradation, comparatively with the sulphuric acid one. In fact, the overall sugar yield was found systematically higher than 93% for TFA hydrolysis, whereas that corresponding to H2SO4 treatment never exceeded 77%. The sugar composition of both pines was found very similar and the sulfidity level (from 10 to 55%) did not affect the pulp sugar composition. The glucose/mannose and xylose/arabinose ratios were found to be around 3.5 for both Portuguese and Nordic pines. Finally, kraft pulping of Pinus pinaster was found to affect drastically galactose, mannose and arabinose.
- Avaliação da qualidade do papel produzido com fibras de Acacia sppPublication . Santos, António; Anjos, Ofélia; Simões, RogérioCom o presente trabalho pretende-se aprofundar o conhecimento sobre o potencial papeleiro da madeira de Acacia melanoxylon e Acacia dealbata. Para efeitos de posicionamento relativo das matérias primas, utilizaram-se aparas industriais de Eucalyptus globulus. A transformação da madeira em pasta foi realizada através do processo ao sulfato. O comportamento global das três espécies nos processos de cozimento e branqueamento é semelhante. No entanto, face à amostra de Eucalyptus globulus usada, a Acacia melanoxylon exibe um rendimento em pasta ligeiramente superior, o que está de acordo com os teores de lenhina e extractivos das madeiras. Para avaliar o potencial das pastas branqueadas na produção de papel, estas foram submetidas ao processo de refinação, em PFI, tendo-se obtido suspensões de pastas com resistência à drenagem crescentes. Posteriormente, caracterizou-se a suspensão fibrosa e o potencial papeleiro. Para o mesmo nível de refinação, os papéis produzidos com fibras de acácia apresentam valores superiores de lisura, índice de tracção e índice de rebentamento. Por outro lado, as fibras da Eucalyptus globulus apresentam maior resistência intrínseca e têm potencial para produzir papeis mais resistentes, embora à custa de maior consumo de energia na refinação. Para um dado nível de resistência mecânica, as características ópticas dos papéis são semelhantes.
- Energy efficiency in low consistency refining: a study using a Valley beaterPublication . Vaz, Álvaro; Espírito-Santo, António; Araújo, Pedro; Simões, Rogério; Silvy, JacquesThe purpose of this work was to study the influence of pulp fiber suspensions refining operating variables on energy efficiency coefficient. Three chemical pulps with different average morphological characteristics were used, obtained from bleached kraft Pinus sylvestris, Eucalyptus globulus and Betula verrucosa. The final objective was to establish the chemical pulps refining efficiency parameters. Refining hydromechanics and energy consumption profiles were analyzed. Average normal and tangential forces on pulp suspension in the gap clearance, resulting rotor-stator distance and no-load and refining conditions power consumption were obtained. The refining trials took place in a laboratory Valley beater, and the manipulated variables were charge on the roll and rotor rotation speed. Global relationships for tangential stress and energy efficiencies in terms of rotation speed and rotor-stator gap were obtained. A relationship between energy efficiency and shear stress was obtained. The results have shown that in a Valley beater increased rotor-stator gaps reduce energy efficiency, concomitantly increasing apparent viscosity and reducing shear stress. No-load power was seen to increase with crowding factor, and thus with flocculation. Inversely, crowding factor and ultimately flocculation had an adverse effect on energy efficiency.
- Optimization of acid sulfite pretreatment in the enzymatic hydrolysis of Cytisus striatusPublication . Vaz, Álvaro; Gomes, Tânia; Simões, RogérioEthanol production from lignocellulosic material includes three major steps: biomass pretreatment, which fragments the lignocellulosic matrix to facilitate the enzymes access to the substrate; hydrolysis, where the polysaccharides are converted into fermentable sugars (e.g. glucose and xylose); and finally, fermentation that produces ethanol or other biologically based chemicals (e.g. lactic acid, succinic acid). The aim of the present work was to study the effect of some operative variables of the pretreatment stage, namely sodium h ydrogen sulfite and sulfuric acid loadings, temperature and time, on the release of sugars in enzymatic hydrolysis, performed applying a Novozymes® cocktail, with fixed charges and operating conditions. Cystisus striatus wood branches were chipped and submitted to different reaction conditions, with a central composite experimental design 2^4+star, exploring the following variables: sulfuric acid charge (0-3%, on wood), sodium bisulfite charge (0-4 %, on wood), maximum temperature (150-190ºC) and time at maximum temperature (0-30 minutes). After pretreatment, the acid hydrolysates were recovered and the solid residues were mechanically disintegrated and thereafter subjected to enzymatic hydrolysis with an enzymatic cocktail from Novozymes®. Sugars and by-products released in the sulfite pretreatment and enzymatic treatment hydrolysates were analyzed by HPLC. The percentage of material released in the acid hydrolysates was between 7 and 29.1%. Temperature and sulfuric acid load were the most important tested variables. The inhibition products represented less than 0.9% of the initial wood mass, even for the most severe reaction conditions. Enzymatic hydrolysis of polysaccharides on solid residues resulted in conversions from 6.0 to 68.9%, depending on the reaction conditions used in biomass pretreatment with sulfite and sulfuric acid. The rate of sugars release proved to be high at the beginning, gradually decreasing with contact time. The experimental data analysis using Statgraphics®Plus5 enabled us to obtain correlation expressions and conclude that all study variables influence this phase of the process, mainly temperature and sulfuric acid load. For a given sulfite load, more acidic conditions led to higher sugar release and greater fragmentation of the material, but also higher production of degradation products; moderate sodium bisulfite (1%) and sulfuric acid (2.25%) loads released practically all hemicelluloses in the raw material.
- Enzymatic hydrolysis of Cytisus striatus: acid sulfite pretreatment optimizationPublication . Vaz, Álvaro; Gomes, Tânia; Simões, RogérioEthanol production from lignocellulosic material includes three major steps: biomass pretreatment, which fragments the lignocellulosic matrix to facilitate the enzymes access to the substrate; hydrolysis, where the polysaccharides are converted into fermentable sugars (e.g. glucose and xylose) [1]; and finally, fermentation that produces ethanol or other biologically based chemicals (e.g. lactic acid, succinic acid) [2]. The aim was to study the effect of pretreatment operative variables, namely sodium bisulfite and sulfuric acid loadings, temperature and time, on released sugars in Cytisus striatus enzymatic hydrolysis with a Novozymes® cocktail. Pre-treatment intends lignin and hemicelluloses removal, reduced cellulose crystallinity and lignocellulosic network porosity increase in order to facilitate enzyme access.