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Mass transport of chemicals into wood is important in kraft pulping. This thesis models small wood particles as cylinders and monitors how tritiated water and sulfide diffuse into the water-filled pores. Tritiated water diffusion is Fickian and diffuses completely into the water contained in the wood. Tortuosity values of the aspen and pine are tabulated. As particle size decreases, the tortuosity of the particles increases. As sulfide diffuses into wood, it is occluded from some water filled areas. Charge exclusion is a possible explanation for this. Sulfide and hydroxide transport into wood chips was displayed using indicators for each component. Pictures show sulfide ingress into the chip core faster, thus confirming the diffusion results. Fractionated sawdust was pulped to determine particle size effect on cooking and pulp properties.

A indústria de papel e celulose convive com questões de adequação da oferta à demanda que influenciam na tomada de decisão em vários elos da cadeia produtiva. A pressão por baixos custos requer novos investimentos em tecnologia, normalmente associados ao processo e ao produto. Neste cenário, o objetivo do presente trabalho envolve o estudo da influência de variáveis de processo sobre a composição química da polpa e do licor preto, bem como sobre a formação de ácidos hexenurônicos, na polpação Kraft industrial de Eucalyptus. A metodologia proposta contemplou a realização de 36 polpações (em duplicata), sendo 3 níveis de álcali ativo (14, 17 e 19%), 2 níveis de sulfidez (20 e 30%) e 3 níveis de temperatura (150, 160 e 170oC). As polpas obtidas foram analisadas quanto à composição química, alvura e viscosidade. Os licores gerados no processo foram analisados quanto à composição química e por espectroscopia no infravermelho. Os resultados obtidos indicaram que uma maior sulfidez gera um menor teor de ácidos hexenurônicos na polpa independentemente da carga de álcali empregada. A temperatura exerce forte influência na geração destes ácidos, sendo que a 160°C foram geradas as maiores concentrações de ácidos hexenurônicos na polpa. Ainda com relação à temperatura, observou-se que o número kappa da polpa é reduzido quando a temperatura é elevada. A carga de álcali ativo leva a um aumento na quantidade de ácidos hexenurônicos gerados na polpa e a uma redução do número kappa. A alvura da polpa foi mais elevada para menores teores de ácidos hexenurônicos. A utilização da técnica de espectroscopia no infravermelho não se mostrou aplicável para a determinação dos teores de lignina nos licores de cozimento. / The pulp and paper industries have to manage issues concerning the offer of their products and the needs of different markets. To get this goal several important aspects of the productive chain has to be considered. The achievement of low costs of production requires investments in technologies for both processes and products. In this context, the aim of the present work involves the study of the influence that process parameters exerts in the chemical composition of the pulps and liquors, as well as hexenuronic acids generated in the industrial kraft pulping of Eucalyptus. The experimental work consisted in a factorial planning designed pulping reactions. 36 cookings were performed (in duplicate) with 3 levels of active alkali (14, 17 e 19%), 2 levels of sulfidity (20 e 30%) and 3 levels of temperature (150, 160 e 170oC). The obtained pulps were analyzed in relation to their chemical composition, brightness and viscosity. The black liquors were also analyzed by infrared spectroscopy. The results indicated that the higher sulfidity produced pulps with the lower content of hexenuronic acids, independently of the charge of active alkali employed in the process. The temperature of the pulping process exerted a strong influence in the production of hexenuronic acids, mainly at 160°C. Still considering the temperature, it was observed that occurs a reduction of the kappa number at higher temperatures. The active alkali charge produced an increase in the amount of hexenuronic acids and a decrease in the kappa number of the pulps. It was also observed an increase in the brightness for the pulps with lower amount of hexenuronic acids. Infrared spectroscopy showed not feasible results considering the determination of lignin content in the pulping liquors.

Lignin is one of the main components in wood and during the chemical pulping processes it is degraded and dissolved into the cooking liquor. The current challenge is to meet the need for energy and raw materials, and reform to a more environmentally sustainable society, so there is a great interest in using kraft lignin as a raw material for energy, materials and as source of chemicals. ) To meet this goal, it is essential to obtain kraft lignin with desirable properties. The overall goal of this master thesis project was to understand the relationship between kraft process conditions and the structure and properties of the dissolved lignin. Wood chips of pine, spruce and eucalyptus were pulped with the kraft process at constant temperature and similar alkali charge and sulphidity to different cooking times. From the collected black liquor, the dissolved kraft lignin was precipitated by acidification with sulphuric acid. It was observed that longer cooking time yields more precipitated material, where pine gave the highest yield. There was a significant difference in colour of the precipitated between eucalyptus and the softwood samples. Some the characteristic properties of the collected samples were investigated. Results from the Klason lignin and ionic chromatography showed variation in lignin and carbohydrate composition depending on raw material and cooking time. This was also indicated by results lignin carbohydrate ratio from analytical pyrolysis. However, the analytical pyrolysis data showed that the relative composition of lignin and carbohydrates was similar independent on pulping time and raw material. The sulphur content was higher for eucalyptus lignin compared to the softwood lignin. Pine lignin with the longest pulping time had the highest total phenolic content. Spruce lignin with the longest cooking time had the highest glass transition temperature. / Lignin är en av de största byggstenarna i träd och andra växtmaterial, både till storlek och mängd. Under kemiska massaframställningsprocesser, som sulfatprocessen, bryts strukturen ned och lignin löses ut i kokvätskan. Ligninets värmevärde tas till vara, genom att det förbränns i sodapannan. Med den utmaning som dagens samhälle står inför, där fossila råvaror ska ersättas med förnyelsebara, finns ett allt större intresse att se vilka andra användningsområden som kan finnas för lignin, som grön råvara för energi, material och kemikalier. Det krävs därför kunskap om hur lignin med lämpliga egenskaper ska kunna utvinnas. Målet med detta examensarbete var att undersöka hur vedråvara och koktid under sulftakoket påverkar egenskaper hos det utlösta ligninet. I denna studie kokades vedflis av tall, gran och eukalyptus enligt sulfatprocessen och det utlösta ligninet analyserades efter tre olika koktider. Längre koktid ledde till mer utfällt material. Det var en tydlig skillnad i färg mellan lignin från eukalyptus och de från barrveden, gran och tall Eukalyptusligninet var mörkare med en tydlig grönaktig färgskiftning. Längre koktid medförde även ett mer lättfiltrerbart lignin. Mängden lignin, bestämt som mängd Klason lignin efter sur hydrolys, var högre i utfällningen efter kok av eukalyptus jämfört med efter kok av barrved. Resultaten från den analytiska pyrolysen visar däremot på rakt motsatt förhållande. Enligt den analytiska pyrolysen är det något mindre mängd lignin i utfällningen efter eukalyptuskok. Orsaken kan vara att vid kvantitativ bestämning av lignin som Klason lignin, kommer det oorganiska materialet att fällas ut tillsammans med ligninet, varvid mängden Klason lignin även inbegriper askmängden. Mängden lignin som lösts ut under koket ökar med ökad koktid, men andelen lignin i det utfällda materialet ändras inte med koktiden. Svavelhalten var högre för (utlöst) eukalyptuslignin än för granlignin och talllignin. Talllignin med den längsta koktiden hade den högsta totala halten fenol. Gran lignin med den längsta koktiden hade det högsta värdet på glastransitionstemperaturen.

Kraft pulping, also known as sulphate pulping is a complex process where the wood components are liberated from each other facilitated by chemical reactions. During the pulping process some dissolved and degraded compounds end up together with the spent cooking chemicals in the black liquor. In kraft pulping of hardwood, the black liquor contains substantial amounts of dissolved hemicellulose, especially xylan due to the wood composition. The xylan content is of high value due to its ability to re-deposit by adsorption on cellulose fibres and its tendency to increase pulp strength and yield. In this work, the possibility of introducing xylan rich, hardwood black liquor from the hardwood digester into the softwood digester at the process of SCA – Munksund was studied. The objective was to investigate if hardwood black liquor addition in a softwood cook can increase the yield and pulp strength. The theoretical feasibility of altering the process was investigated by a literature review and a brief process investigation. During the study a total of eight lab cooks were conducted to obtain information on how hardwood black liquor addition changes the pulp quality of regular softwood cooks. The wood chips, white liquor and hardwood black liquor used were collected at Munksund and the process conditions in the lab cooks were chosen to simulate the actual process in the Munksund mill. In addition to the cooking, chemical and physical evaluation on pulps, cooking liquors and wood chips were performed. The theoretical evaluation indicates that the process in Munksund is well suited for introducing the hardwood black liquor in to the softwood digester. The chemical analysis of the black liquors show a xylan content that is approximately four times higher in the hardwood black liquor compared to the softwood black liquor. In the kappa number range of approximately 80-90, a total yield increase of 0.4%-units was obtained for two cooks with hardwood black liquor addition compared to their corresponding reference cooks. A carbohydrate analysis showed a higher xylan content in the pulp cooked with addition of hardwood black liquor compared to the corresponding reference pulp. One pulp with hardwood black liquor addition and its corresponding reference cook were refined in an Escher Wyss lab mill. The pulp with hardwood black liquor addition exhibits an increase or retained strength for all strength evaluation tests made on handmade pulp sheets. Strength increases of approximately 5% were obtained for tensile index and ISO-Z strength for a pulp with hardwood black liquor addition.   The results conducted in this study shows that it can be possible to slightly increase both the yield and some pulp strength parameters when adding hardwood black liquor in to the softwood cook in lab scale. It is also shown that the increase in the total yield most likely depends on xylan adsorption on the cellulose fibres. The calculated increased revenue for this process change could be over 400 000 Euro per year.

Este trabalho teve como objetivo analisar os cavacos de dimensões reduzidas inseridos em cozimentos que se utilizam de menores tempos e maiores temperaturas, de maneira a se obter as bases para o estabelecimento de um novo processo e/ou a otimização dos sistemas atualmente utilizados em escala industrial. Amostras de cavacos de referência (3,6 mm, obtidas pelo processo convencional de picagem) e de cavacos com espessura de 0,5 mm, 1 mm e 2 mm (obtidas por um gerador de partículas), do híbrido de Eucalyptus urophylla x Eucalyptus grandis com 7 anos foram analisadas quanto à densidade básica, composição química e morfologia das fibras. Após a caracterização, os materiais foram submetidos à polpação kraft pelo processo convencional e foram testados três níveis de fator H com quatro níveis de álcali ativo de maneira a se estabelecer uma equação que representasse o processo e pudesse ser utilizada em cozimentos futuros. Através das equações obtidas foi possível calcular os parâmetros de rendimento depurado, álcali ativo residual, álcali ativo consumido, teor de sólidos secos, fator H e álcali ativo em função de um número kappa 18. Os resultados mostram que a densidade básica, a composição química e a morfologia das fibras da madeira não foram afetadas pelo processo de picagem. No entanto, a densidade a granel foi afetada pela espessura dos cavacos, sendo de 0,037, 0,081, 0,110 e 0,141 g.cm-³ para os cavacos de 0,5 mm, 1 mm, 2 mm e 3,6 mm respectivamente. No processo de polpação, as espessuras se comportaram de maneira semelhante, no entanto, a espessura de 2 mm apresentou o melhor número kappa para o fator H de 451, o de maior interesse, com o mesmo rendimento que as demais espessuras. Na análise de regressão, a espessura de 2 mm apresentou melhor rendimento, menor teor de sólidos e menor fator H (de 461), compatível com o que se pretende utilizar em processos de polpação com tempo reduzido de cozimento. / The objective of this work was to evaluate the performance of thin chips inserted on a short time and higher temperatures in cooking process, to obtain the basis for the establishment of a new process and / or the optimization of the currently systems used on an industrial scale. Samples of the reference chips (3,6 mm obtained by the conventional process of chipping) and thin chips with 0,5 mm, 1 mm and 2 mm (obtained by a particle generator) of the Eucalyptus urophylla x Eucalyptus grandis hybrid with 7 years of age had their density, chemical composition and fibers morphology evaluated. After the characterization, the materials were submitted to conventional kraft pulping process and three levels of H factor with four levels of active alkali were tested to establish an equation to represent the process that can be used on future cookings. Yield, residual active alkali, consumed active alkali, dry solids, H factor and active alkali were calculated through equations, according to a kappa number 18. The results show that the basic density, chemical composition and morphology of the wood fibers were not affected by the chipping process. However, the bulk density of 0,037, 0,081, 0,110 and 0,141 g.cm-³ for the 0,5 mm, 1 mm, 2 mm and 3,6 mm chips, respectively, was affected by the chip thickness. On the pulping process, the different chips had the same behavior, however, 2 mm chips showed the best kappa number to H factor 451, with the same yield as the other thickness. On the regression analysis, the 2 mm chips showed better performance, lower solids content and lower H factor (461), consistent with a short time pulping process.

O presente trabalho teve como objetivo avaliar a utilização das madeiras de Corymbia citriodora, Corymbia torelliana e seus híbridos para a produção de celulose kraft branqueada. Para isso, as madeiras destas espécies e híbridos foram caracterizadas tecnologicamente e submetidas ao processo kraft de polpação e branqueamento, sendo comparadas à madeira de E. grandis x E. urophylla, utilizada como referência tecnológica. Ao todo, foram avaliadas sete diferentes materiais genéticos do gênero Corymbia: dois materiais de C. citriodora, com 8 e 18 anos de idade, um material de C. torelliana, com 15 anos, e quatro híbridos destas espécies, com 7 anos de idade. A madeira de E. grandis x E. urophylla apresentava 6 anos de idade. Inicialmente, as madeiras das diferentes espécies e híbridos foram caracterizadas sendo, em seguida, submetidas a um processo modificado de polpação kraft. As polpas foram deslignificadas com oxigênio e branqueadas através da sequência DA Ep D1 P visando alvura final de 89,5 ± 0,5% ISO, e tiveram suas características físico-mecânicas determinadas. O impacto das diferentes madeiras no dimensionamento de uma fábrica de celulose também foi avaliado. Os resultados mostram que as madeiras do gênero Corymbia apresentam alta densidade básica e baixo teor de lignina, além de fibras com maior comprimento, menor largura, menor diâmetro do lume, maior espessura de parede e maior fração parede em relação à madeira de E. grandis x E. urophylla. Os processos de polpação de C. citriodora (madeira de 8 anos) e E. grandis x E. urophylla demandam menor carga alcalina e fator H, resultando nos maiores rendimentos, sendo que os menores consumos específicos de madeira foram observados para as madeiras de C. citriodora. A deslignificação com oxigênio é mais eficiente para as polpas do gênero Corymbia em comparação à polpa de E. grandis x E. urophylla. No branqueamento, as polpas C. citriodora (madeira de 8 anos) e E. grandis x E. urophylla são as que demandam menor aplicação de reagentes químicos para atingir determinada alvura. Em comparação às polpas das demais espécies e híbridos avaliadas, as polpas branqueadas da espécie C. citriodora apresentam alto volume específico, baixa resistência à passagem do ar, alta capilaridade, baixo índice de retenção de água e alta resistência ao rasgo, características que recomendam a utilização da polpa desta espécie para a produção de papéis de alta absorção (tissue). Já as polpas de C. torelliana x C. citriodora apresentam baixo volume específico, alta resistência à passagem do ar e baixa capilaridade, enquanto as polpas de E. grandis x E. urophylla e de um dos materiais de C. citriodora x C. torelliana se destacam por apresentar as maiores resistências à tração, rasgo e estouro. No dimensionamento de uma fábrica de celulose, as madeiras dos híbridos de C. citriodora e C. torelliana que apresentam a espécie C. torelliana como genitor feminino (C. citriodora x C. torelliana) demandam maior atenção, principalmente nas áreas da caldeira de recuperação e caustificação, uma vez que apresentam alta demanda de álcali e alta geração de sólidos em comparação aos demais materiais genéticos. / The present work aimed to evaluate the use of the woods of Corymbia citriodora, Corymbia torelliana and their hybrids on bleached kraft pulp production. Woods from these species and hybrids were technologically characterized and submitted to kraft pulping process and bleaching. These woods were compared to E. grandis x E. urophylla, which was used as technological reference. Seven different genetic materials from Corymbia were analyzed: two materials of C. citriodora, with 8 and 18 years-old, one material of C. torelliana, with 15 years-old, and four hybrids of these species, with 7 years-old. The wood of de E. grandis x E. urophylla had 6 years-old. Initially, the different woods were technologically characterized and then submitted to a modified kraft pulping process. The pulps were delignified with oxygen and bleached through a DA Ep D1 P bleaching sequence until 89,5 ± 0,5% ISO of brightness. The bleached pulps had their physical-mechanical characteristics evaluated. The impact of these different woods in a pulp mill dimensioning was also evaluated. The results show that the woods of Corymbia genus present high basic density, low lignin content and fibers with higher length, lower width, lower lumen width, higher wall thickness and higher wall fraction if compared to E. grandis x E. urophylla. The pulping of C. citriodora and E. grandis x E. urophylla demands lower alkali charge and H factor, resulting in higher yields, while the lowest wood specific consumption was observed to C. citriodora\'s woods. The oxygen delignification is more efficient for Corymbia\'s pulps than for E. grandis x E. urophylla. On bleaching, the pulps of C. citriodora (wood with 8 years-old) and E. grandis x E. urophylla are those that demand the lowest chemical reagents charges to achieve the determined brightness. The bleached pulps of C. citriodora present high specific volume, low air passage resistance, high capillarity, low water retention value and high tear index. Based on these characteristics it is possible to recommend this species to tissue papers production. The pulps of C. torelliana x C. citriodora present low specific volume, high air passage resistance and low capillarity, while the pulp of E. grandis x E. urophylla and one of the hybrids of C. citriodora x C. torelliana stands out for presenting the higher tensile, tear and burst indexes. In a pulp mill dimensioning, the woods of C. torelliana x C. citriodora demands higher attention, mainly on recovery boiler and causticizing, for presenting high alkali demand and high solids generation in comparison to the other genetic materials.

The kraft pulping process has been known for decades. The focus in kraft pulping has always been on better operation of the chemical recovery system. One of the targets is on deadload (sodium sulfate (Na2SO4) and sodium carbonate (Na2CO3)) reduction in white liquor. A model based on several literature references was developed to study the effect of deadload reduction. A base model was developed based on current mill operation. This base model was compared to the deadload reduction model. Overall improvement, such as operating cost saving and revenue generation was achieved from deadload reduction. Operating cost saving involves less deadload chemical in chemical recovery system, and less water that was associated with the deadload itself. Revenue generation involves generating more steam and heat from the recovery boiler that can be used for mill purposes or energy revenue. Two important variables to achieve deadload reduction are causticizing efficiency and reduction efficiency.

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