This study first examined the kinetic changes of fiber carboxyl group content in bulk fiber, polysaccharide, and residual lignin of oxygen delignified pulps during one-stage oxygen delignification of a low kappa (32.5) kraft pulp. The carboxyl group contents determined in different chemical components of oxygen delignified pulps was used to establish the distribution of carboxyl groups in lignin and pulp polysaccharide and decouple the responses from residual lignin and polysaccharide. Following this study, two high kappa (~ 49.0) SW kraft pulps prepared were delignified through two-stage oxygen delignification. Fiber carboxyl group profiles of these pulps were elucidated to investigate the effect of lignin content of incoming unbleached kraft pulps on fiber carboxyl group formation. Due to a limitation to enhance fiber carboxyl groups only by parameter optimization during one- and two- stage oxygen delignification, a catalytic oxidation program was developed to enhance fiber carboxyl groups by 52.2 116.0 % employing 0.10 - 0.18% of a bismuth ruthenium pyrochlore oxide catalyst during oxygen delignification. The mechanism of fiber carboxyl group formation through the catalytic oxidation was proposed. The main factor on carboxyl group formation in pulp carbohydrate was identified to follow the order: NaOH > oxygen pressure> reaction temperature through a 3-factor at 3-level (L933) orthogonal experimental design and the optimal conditions were found at 2.5% NaOH, 85-100 oC, and 800-960 kPa O2 during the catalytic oxidation. ECF bleaching study was also conducted on these pulps with higher amount of fiber carboxyl group enhanced at early pulping and oxygen delignification processes. The bleaching results demonstrated that the early-stage enhanced fiber carboxyl groups were partially retained through ECF bleaching. Additionally, fiber carboxyl groups of fully bleached kraft pulps were ~ 20% different from typical bleaching protocols, depending on bleaching chemicals used and the bleaching sequences such as DEDED, (D+C)EDED, ODEDD, and OQPZP. This study finally demonstrated that an increase of fiber carboxyl groups by 17.4-62.1% through chemical oxidation resulted in reduced fiber curl, increased fiber WRVs, 4.3-25.5 % increase in paper tensile index at comparable pulp viscosity; and 4.4 -30.1% increase in paper dry tensile stiffness.

The objective of this study was to investigate the possibility of recycling enzymes during saccharification of cellulose for the production of ethanol from woodchips. To make enzyme recycling feasible and economical when woodchips are processed for ethanol, the lignin in the wood is to be removed before the enzymes are added. Since enzymes constitute a major part of the input costs, second only to the feedstock, the ability to reuse the enzymes could lead to a considerable decrease in the production cost of ethanol. Tulip poplar woodchips were selected as the feedstock. Different delignification methods with recovery of byproducts were investigated. Alkali extraction, using dilute NaOH for the removal of lignin after steam pretreatment, was used as the base case against which all other processes were compared. Recovery of furfural and methanol, produced during the pretreatment of the woodchips, for sale as byproducts was one modification to the alkali extraction process that was investigated. The conversion of xylose to furfural and the recovery of the furfural as a byproduct was the third case explored. Solvent extraction using a 50:50 ethanol-water mixture instead of extraction with NaOH was the fourth case examined. Process flow sheets were then developed to recycle the enzymes during the hydrolysis and fermentation of this prehyrolyzed and delignified wood. Two reactor setup schemes were examined for enzyme recycling. One scheme involved a single train of reactors, with the whole pretreated slurry flowing from one reactor to the next, whereas, in the other scheme, the slurry was split among parallel trains of reactors. The activity loss of the enzymes was modeled such that a part of the enzymes entering the reactor lost all their activity. The loss of activity in multiple steps, with enzymes losing only some of their activity, was also modeled. Here the enzymes entering the reactor constituted a mixture with different activities instead of all the enzymes having the same activity like in the previous single step model. Recovering methanol and furfural reduced the minimum ethanol selling price. High temperature ethanol water pretreatment and lignin extraction reduced the minimum ethanol selling price compared to the base case of steam pretreatment followed by alkali extraction. Enzyme recycling also reduces the minimum ethanol selling price. The magnitude of the price reduction depends on the recycling scheme selected and the rate of enzyme deactivation, which has not been measured.

Submitted by LUIZ MARCIO MACHADO SUARDI JUNIOR null (luizsuardi@hotmail.com) on 2016-03-22T13:51:29Z No. of bitstreams: 1 Dissertação - SUARDI JUNIOR, L. M. M..pdf: 1321070 bytes, checksum: 9c1423b93b2aa02e238aedb6532c686d (MD5) / Approved for entry into archive by Sandra Manzano de Almeida (smanzano@marilia.unesp.br) on 2016-03-22T18:16:18Z (GMT) No. of bitstreams: 1 suardijunior_lmm_me_bot.pdf: 1321070 bytes, checksum: 9c1423b93b2aa02e238aedb6532c686d (MD5) / Made available in DSpace on 2016-03-22T18:16:18Z (GMT). No. of bitstreams: 1 suardijunior_lmm_me_bot.pdf: 1321070 bytes, checksum: 9c1423b93b2aa02e238aedb6532c686d (MD5) Previous issue date: 2016-02-05 / O presente trabalho teve por objetivo realizar um estudo comparativo das características dendrométricas e da qualidade da madeira entre as espécies de Pinus taeda, Pinus elliottii, Pinus tecunumanii, Pinus maximinoi e o híbrido de Pinus elliottii var. elliottii x Pinus caribaea var. hondurensis (PECH), provenientes de primeiro desbaste com 6,5 anos de idade, destinadas à produção de celulose. O delineamento experimental foi o inteiramente casualizado (DIC) composto por 20 árvores (5 espécies x 4 repetições), portanto, foram coletadas 4 árvores por espécie de DAP médio determinado por inventário piloto. De cada árvore foram retirados 6 discos com espessura de aproximadamente 5cm, nas posições do DAP, 0 % (Base), 25 %, 50 %, 75 % e 100 % da altura comercial. Foram avaliados os parâmetros dendrométricos: DAP, altura total e comercial, volume comercial sem casca e massa seca comercial por árvore; a densidade básica a composição química e a polpação kraft. Os resultados demonstraram que o híbrido PECH apresentou os maiores valores para os parâmetros dendrométricos, sendo estatisticamente superior às demais espécies para o parâmetro DAP (17,7 cm). O Pinus elliottii foi significativamente inferior para o volume comercial sem casca. A densidade básica da madeira não apresentou diferenças significativas, provavelmente devido a pouca idade das árvores. A espécie de PECH apresentou os piores rendimentos de polpação e consumo específico de madeira. Isso pode ter ocorrido devido o maior valor para o teor de lignina (30,25 %) e elevado teor de extrativos (4,71 %) apresentado pela espécie, e também pelo menor valor para a densidade básica da madeira (0,339 g cm-3). Considerando o uso da madeira de primeiro desbaste para produção de celulose, pode-se concluir que das espécies utilizadas nesse estudo, apenas a madeira do híbrido de Pinus elliottii var. elliottii x Pinus caribaea var. hondurensis foi desfavorável por apresentar o menor rendimento bruto e maior consumo específico de madeira. / This study aimed to carry out a comparative study of dendrometric characteristics and quality of wood between species of Pinus taeda, Pinus elliottii, Pinus tecunumanii, Pinus maximinoi and hybrid Pinus elliottii var. elliottii x Pinus caribaea var. hondurensis (PECH), from first thinning with 6.5 years of age for the production of cellulose. The experimental was completely randomized design (CRD) consists of 20 trees (5 species x 4 repetitions) therefore were collected 4 trees per species average DBH determined by pilot inventory. Each tree were removed six discs with thickness of approximately 5 cm, the DBH positions, 0 % (basis), 25 %, 50 %, 75 % and 100 % of the commercial height. We evaluated the dendrometric parameters: DBH, total and commercial height, trade without shell and commercial dry mass per tree; basic chemical composition and density of the kraft delignification. The results showed that the hybrid PECH showed the highest values for the dendrometric parameters being statistically superior to the other species for the DBH parameter (17.7 cm). The Pinus elliottii was significantly lower for the commercial volume without bark. The basic wood density showed no significant differences, probably due to the young age of the trees. The kind of PECH showed the worst pulping yields and specific consumption of wood. This may have occurred because the greatest value for the lignin content (30.25%) and high content of extractives (4.71 %) presented by the species, and also at the lower for basic wood density (0.339 g cm-3). Considering the use of the first thinning wood for pulp production, it can be said that the species used in this study, only wood of hybrid Pinus elliottii var. elliottii x Pinus caribaea var. hondurensis was unfavorable due to the lower gross income and higher specific consumption of wood.

A casca de coco verde (Cocos Nucifera L.) é um resíduo lignocelulósico amplamente disponível na região Nordeste do Brasil e de grande preocupação ambiental devido ao seu volume elevado. Mas, os materiais lignocelulósicos podem ser recursos renováveis e abundantes para obtenção de açúcares após passarem por hidrólise enzimática da celulose e hemicelulose. Para uma eficiente hidrólise é necessário romper a rede lignocelulósica que circunda fisicamente as fibras de celulose dificultando contato entre celulose e enzima. Os tratamentos tradicionais de deslignificação que empregam condições drásticas de temperatura e pH levam à formação de alguns compostos que limitam o uso desses hidrolisados em processos biotecnológios pois inibem a ação microbiana. O tratamento com CO2 supercrítico pode ser operado em condições amenas de pH e temperatura evitando o problema da formação destes inibidores. Portanto, o objetivo geral desse trabalho foi a obtenção de açúcares redutores a partir da fibra da casca do coco verde por meio de hidrólise enzimática da fibra prétratada com CO2 em condições supercríticas. Foram estudadas sete condições de extração em que se variou o tempo de contato do CO2 com a fibra de coco (3 e 5 horas), modificador de polaridade (NaOH, NaHSO4 e etanol) e manteve-se constante a extração dinâmica por 1 hora seguida de despressurização rápida no final do processo. A eficiência da extração com CO2 supercrítico para deslignificação da fibra de coco verde foi baseada na caracterização da fibra pela composição lignocelulósica, imagens de microscopia eletrônica de varredura e análise qualitativa da composição lignocelulósica por espectroscopia de infravermelho com transformada de Fourier e a quantificação de açúcares redutores. A fibra de coco apresentou teores de lignina, celulose e hemicelulose de 26,66, 46,37 e 16,18 g/100g de fibra de coco verde seca, respectivamente. Para hidrólise enzimática utilizou-se uma enzima comercial composta de três enzimas principais: celulases, hemicelulases e β-glucosidases em dois tempos de hidrólise (24 e 72 h) e duas concentrações enzimáticas (6 e 30g de enzima/g de celulose total no substrato) para que fossem avaliadas as situações de aplicação comercial e condições de rendimento máximo. O tratamento com CO2 supercrítico provocou alterações na estrutura física e química da fibra, aumentando a porosidade e diminuindo o teor de compostos fenólicos e ceras e também afrouxamento das ligações de hidrogênio caracterizando a deslignificação da fibra de coco verde. No entanto, a extração com CO2 supercrítico não causou aumento significativo da obtenção de açúcares redutores após hidrólise enzimática da fibra de coco. A hidrólise enzimática realizada em 72h gerou aumento em até 134% no teor de açúcares redutores em relação a hidrólise com 24h de reação para a mesma concentração enzimática (30%). A hidrólise enzimática (72h e 30% de enzima) da fibra de coco verde in natura apresentou bons valores de açúcares redutores (532,27 µmol de glicose/g de fibra de coco seca), podendo ser uma nova utilização para o material lignocelulósico do coco verde que é subaproveitado. Os açúcares redutores obtidos da fibra de coco verde in natura podem passar por processo de purificação e isolamento de algum açúcar de interesse econômico ou ser utilizado em processos que açúcares redutores são necessários como substrato para fermentação por Saccharomyces cerevisiae na produção de álcool, por exemplo. / The coconut husk (Cocos nucifera L.) is a lignocellulosic byproduct widely available in the Brazilian Northeast region and due its high volume is a reason of huge environmental concern. But the lignocellulosic materials are renewable and abundant resources of sugars after submitted to enzymatic hydrolysis of cellulose and hemicellulose. For efficient hydrolysis is necessary to break the lignocellulosic netting that physically surrounds the cellulose fibers hindering contact between the enzyme and cellulose. The traditional delignification treatment employing drastic conditions of temperature and pH lead to the formation and release of some compounds that limit the hydrolysates use in biotechnological processes since it inhibits microbial action. The treatment with supercritical CO2 can be operated at lower temperatures avoiding inhibitors formation. Therefore, the aim of this study was to obtain reducing sugars from the husk coconut fiber through enzymatic hydrolysis of pretreated fiber with CO2 in supercritical conditions. Seven extraction conditions were studied varying the CO2 contact time with the coconut fiber (3 and 5 hours), polarity modifier (NaOH, NaHSO4 and ethanol) and maintaining as constants the dynamic extraction time (1 hour) and rapid depressurization at the end of process. The efficiency of extraction with supercritical CO2 to green coconut fiber delignification was based on the characterization of the fiber by the lignocellulosic composition, images of scanning electron microscopy and qualitative analysis of lignocellulosic composition spectroscopy infrared with Fourier transform and quantification of reducing sugars. Green coconut fiber presents lignin, cellulose and hemicellulose contents of 26.66, 46.37 and 16.18 g/100 g of dry coconut fiber, respectively. For enzymatic hydrolysis used a commercial enzyme composed of three major enzymes: cellulase, hemicellulase and β-glucosidases in two hydrolysis time (24 h and 72) and two enzymatic concentrations (6 and 30 g enzyme / g cellulose in total substrate) to be evaluated situations of commercial application and conditions de maximum yield. Treatment with supercritical CO2 caused changes in the physical and chemical structure of the fiber, increasing the porosity and decreasing the level of phenolic compounds, waxes and hydrogen bonds attenuation causing the delignification of coconut fiber. However, extraction with supercritical CO2 didn\'t significant increase reducing sugars fiber contents after enzymatic hydrolysis. Enzymatic hydrolysis performed in 72h caused up to 134% increase in reducing sugars compared to smaller hydrolysis time (24) for enzyme concentration of 30%. In general, enzymatic hydrolysis (72 hours and 30% of enzyme) of natural coconut fiber showed good values of reducing sugars (532,27 µmol glucose/g de dry coconut fiber) and may be used as a new lignocellulosic material from coconut which is underused. Reducing sugars obtained from natural coconut fiber can pass through purification process of purification of some sugar of interest economic or be used in processes that reducing sugars are necessary as a substrate for fermentation by Saccharomyces cerevisiae, as example in alcohol production.

O uso do bagaço de cana-de-açúcar, um subproduto da produção sucroalcooleira, ainda está hoje atrelado diretamente à produção de energia com sua queima nas usinas, um uso que é pouco nobre, considerando-se a grande diversidade de compostos químicos presentes neste tipo de material. A possibilidade de valorização desta matéria-prima lignocelulósica está ligada a realização de etapas de separação das principais frações de compostos, a celulose, as hemiceluloses e a lignina. Neste contexto, as deslignificações organossolve, etapa de remoção da lignina através da solubilização da mesma em soluções orgânicas, tem grande potencial de uso, visto que nestas pode-se recuperar tanto a polpa como o licor de polpação para posterior uso. Assim, verifica-se que a solubilidade da lignina é o fator que diferencia a utilização de um dado solvente orgânico em uma deslignificação organossolve. Desta maneira, pode-se utilizar o conceito de parâmetros de solubilidade para a escolha de um melhor solvente para o processo. Neste trabalho, verificou-se a relação entre a deslignificação organossolve e a distância e afinidade de um solvente com a esfera de solubilidade de Hansen para a lignina de bagaço de cana-de-açúcar. Verificou-se que os parâmetros de solubilidade de Hansen para a lignina verificados na literatura não apresentam boa correlação com os dados de deslignificação, porém, uma nova esfera de solubilidade foi desenvolvida, na qual verificou-se um coeficiente de determinação de 0,93856, em detrimento de um de 0,72074 para a esfera de solubilidade verificada na literatura. Concluiu-se que o modelo desenvolvido possuía como principal diferença com relação ao modelo obtido por Hansen e Björkman para a lignina, um parâmetro de solubilidade para interações intermoleculares polares (δp) inferior e um parâmetro de solubilidade para a capacidade de realização de ligações de hidrogênio (δh) bem superior, porém mantendo o mesmo parâmetro de solubilidade total (δ). Confirmou-se a relação entre a deslignificação e os valores de distância e de afinidade obtidos neste trabalho, com a realização de deslignificações usando misturas ternárias e quaternárias com solventes de baixo custo e/ou excedentes no mercado (etanol, glicerol e 2-butanol, além de água). Concluiu-se que apesar da esfera de solubilidade desenvolvida permitir melhor ajuste dos dados, não se pode afirmar que esta é com certeza a esfera real para a lignina. / The use of sugarcane bagasse, a by-product of sugar and ethanol production, is still linked today directly to energy production with its burning in power plants, a use which is not very noble, considering the great diversity of chemical compounds present in the lignocellulosic matrix. The possibility of better use of lignocellulosic feedstock is linked to steps of separation of their main fractions, cellulose, hemicelluloses and lignin. In this context, organosolv delignification, in which lignin is removed by the solubilization in organic solutions have great potential, since both pulps and the pulping liquor can be recovered for later use. Thus, since the solubility of lignin is the factor that differentiates the use of a given organic solvent in an organosolv delignification, the concept of solubility parameters can be used for the selection of the organic solvent. In this dissertation the relationship between the distance and the affinity of a solvent with the Hansen sphere of solubility for lignin from bagasse cane sugar and organosolv delignification were studied. It was found that the Hansen solubility parameters for lignin found in the literature do not present a good correlation with delignification data. Thus a new sphere of solubility was developed, with a determination coefficient of 0.93856, over a determination coefficient of 0.72074 for the sphere of solubility found in the literature. It was concluded that the main differences between the developed model and the model obtained by Hansen and Björkman for lignin were a lower solubility parameter for polar intermolecular interactions (δp) and a higher solubility parameter for hydrogen bonds (δh), however keeping the same total solubility parameter (δ). The relationship between delignification and the values of the distance and affinity obtained in this work were confirmed with the attainment of organosolv delignification using tertiary and quaternary mixtures of solvents with low cost and/or availability in the market (ethanol, glycerol and 2-butanol, in addition to water). It was concluded that although the developed solubility sphere allowed a better fit of the data, it cannot be stated with certainty that this is the real sphere for lignin.

Rapporten presenterar en studie där tre trätyper, balsa, ask och björk, fabriceras genom en förutbestämd metod till transparent trä. Detta material har många möjliga applikationer, inklusive energieffektiva byggnader, förpackningar, solceller och elektroniska apparater. Syftet med studien är att jämföra de erhållna proverna av transparent trä utifrån morfologi och optiska egenskaper samt koppla dessa resultat till mikrostruktur. Detta för att avgöra huruvida den specifika fabriceringsmetoden lämpar sig för trätyperna och vilken som är mest lämpad. Den valda fabriceringsmetoden består av tre steg, delignifiering, tvätt med lösningsmedel samt polymerinfiltration. Syftet med det första steget i processen, delignifieringen, är att ta bort lignin, beståndsdelen i trä som ger träet dess färg. Detta skedde genom kemikaliebehandling med acetatbuffer och natriumklorit i sur miljö under uppvärmning, varvid träproverna blev vita. Proverna placerades därefter i en vakuumdesickator där de tvättades med etanol och därefter aceton. Etanol hindrar fibrerna från att krympa och acetonet tar bort de sista kemikalieresterna i trästrukturen. Inför det sista steget, polymerinfiltrationen, polymeriserades monomerer av metylmetakrylat till oligomerer, varpå dessa pressades in i träproverna med vakuum där de polymeriserades till polymetylmetakrylat (PMMA). PMMA har ett liknande brytningsindex till trä, vilket minskar ljusspridningen och ökar transparensen i provet. Vidare placerades träproverna mellan två glasplattor och lindades in i aluminiumfolie. Proverna värmdes i ugn där polymeriseringen slutfördes och det transparenta träet erhölls. Träprovernas optiska egenskaper och morfologi karakteriserades. För att bestämma optiska egenskaper uppmättes transmittans och haze. Transmittansen anger hur mycket ljus som kan passera genom provet, medan haze anger hur mycket ljusspridning som sker i förhållande till transmittansen. Dessa parametrar uppmättes enligt ASTM D1003 “Standard Method for Haze and Luminous Transmittance of Transparent Plastics”. Provernas morfologi karakteriserades med ett svepelektronmikroskop (SEM) och resultaten presenterades med högupplösta bilder. Från dessaanalyserades mikrostrukturen i träproverna och graden av delignifiering och polymerinfiltration bedömdes. Resultaten från mätningarna av de optiska egenskaperna visade att balsa har den högsta transmittansen (81–87%), följt av björk (74–83%) och sedan ask (66–78% för sommarved och 74–83% för vårved). Vidare uppmättes haze till ca 65–70% för balsa, ca 70–75% för björk och 74-80% för ask. Genom analys av SEM-bilderna bedömdes graden av delignifiering som högst i balsaträet. För att avgöra detta studerades mellanrummet mellan fibrerna som i obehandlat trä är ligninfyllda. Det observerades då att dessa mellanrum var mest tomma i det delignifierade balsaträt, vilket antydde på att graden av delignifiering var högst för denna trätyp. Graden av polymerinfiltrering ansågs likvärdig för de tre träsorterna då det förekom luftfickor i samtliga träprov. Sammanlagt ledde detta till att balsa blev mest transparent av de tre träsorterna, och är den mest lämpade träsorten för denna fabriceringsmetod.

Esteves et.al. 2020 visade att syrgasdelignifiering ökar den totala fiberladdningen men leder inte alltid till ökad pappersstyrka. Denna studie syftar till att undersöka hur fiberladdning påverkar massans egenskaper.  För att testa hypotesen att ökningen av dragstyrkan beror på den större mängd sekundärt finmaterial som orsakas av malningen, testades vissa egenskaper hos massan, såsom vattenabsorption, med och utan malning avmassan. Två kraftmassor med olika initialt kappatal, 91 respektive 52, syrgasdelignifierades med olika alkalilsats under varierad tid. De massor som hade den lägsta och högsta mängden totala fiberladdningar maldes med PFI-kvarn. Water Retention Value (WRV), Schopper-Riegler (SR), Fiber Saturation Point (FSP) och finmaterial analyserades. WRV testades också efter att finmaterialet avlägsnats från massan.  Resultaten tyder på att massan med en större ökning av den totala fiberladdningen jämfört med den kraftkokta massan vid ett givet kappantal kan resultera i en högre ökning av FSP och WRV. Massor med större ökning av den totala fiberladdningen bildade mer finmaterial vid malning, vilket resulterar i en högre ökning av SR. / According to a previous study from Esteves et. al. 2020, it was found that oxygen delignification can increase the total fiber charge but does not always increase the paper strength. This study aims to investigate how fiber charge has an impact on pulp properties.  To test the hypothesis that the increase in mechanical strength for the fiber is due to the bigger increase of secondary fines caused by the refining process, some properties of the pulp such as water holding capacity were tested with different treatments: refining and no refining. Two kraft cooked pulp with different initial kappa numbers of 91 and 52 were subjected to oxygen delignification with different alkali charges and reaction times. When the characterization tests such as, kappa number and total fiber charge measurement have been determined, the samples which had the lowest and the highest total fiber charge were PFI refined and other analysis such as, water retention value (WRV), Schopper-Riegler degree (SR), fiber saturation point (FSP), and fine content, were done. WRV was also tested without fines.  The results suggest that the pulp with a higher increase in total fiber charge when compared to the kraft cooked pulp at a given kappa number can result in a higher increase in FSP and WRV. A higher increase in total fiber charge can also have a high tendency to create fines, due to the higher swelling ability, resulting in a higher increase in SR.