HexA Content Research Articles

Stoichiometry of reactions of ozone and hypochlorous acid with lignin and hexenuronic acid and its chlorination

The stoichiometry of ozone and hypochlorous acid reactions with lignin and hexenuronic acid (HexA) was measured in bleaching experiments of Eucalyptus sp. kraft pulp. The progress of the reactions was followed by UV Resonance Raman spectroscopy that can quantify lignin and HexA based on the Raman scattering intensities of the carbon–carbon double bond in HexA and the aromatic ring in lignin. Here, one mol of ozone converted 0.16 mol of lignin (C9 monomer units) and 0.28 mol of HexA, whereas 1 mol of hypochlorous acid converted 0.09 mol of lignin and 0.23 mol of HexA. The use of a tertiary amine catalyst with the hypochlorous acid treatments did not affect these stoichiometries. The stoichiometric ratios showed that ozone was more efficient in oxidizing lignin than hypochlorous acid, while both electrophiles reacted with HexA to a similar extent. HexA reaction by hypochlorous acid was concluded to involve initial electrophilic chlorination of the carbon–carbon double bond, contributing to significant organochlorine (OX) formation in the pulp. Evidence on this was the linear correlation between the initial HexA content and OX (0.59 mol OX per mol HexA) and the high OX content in the xylan extracted from the bleached pulp. The 2D NMR HSQC and TOCSY spectra of the isolated xylans showed the disappearance of HexA signals after the treatment with hypochlorous acid and the appearance of a new spin system, yet to be fully identified.

Evaluating the potential of ozone in creating functional groups on cellulose

Several eucalyptus pulps (85% of cellulose) with different lignin and HexA content (unbleached, TCF and ECF) as well as cotton linters (97% of cellulose) were treated with ozone (at different pH and ozone doses) in order to modify its fibre-components. Special interest was given in the introduction of functional groups in carbohydrates. The presence of these groups was mainly identified by the chain scissions due to carbonyl groups (CSC=O) produced in cellulose during viscosity measurement. At a dose of 0.5% odp of ozone, the greatest amount of CSC=O (0.5) was created at acidic pH and with the ECF pulp, followed by the TCF (0.3) and by the unbleached (0.2). The same CSC=O (0.2) was obtained in cotton pulp. In this pulp, the ozone concentration had to be increased for the treatment to be effective. A further increase in the accessibility in both pulps was achieved by applying a washing stage between two ozone stages at 0.5% (0.5 + 0.5). With this treatment, the CSC=O was increased to 5.3 in the ECF, to 0.8 in the TCF and only to 0.3 in cotton. Brightness reversion and the amount of DNPH consumed were also used to verify the presence of functional groups. At 0.5 + 0.5, brightness reversion was increased from 16 to 55% in ECF, from 27 to 46% in TCF and from 7 to 31% in cotton. Therefore, it is shown that functional groups can be introduced by ozone in carbohydrates, but this effect strongly depends on the lignin, HexA and hemicellulose content.Graphical abstract

Partial exchange of ozone by electron beam irradiation shows better viscosity control and less oxidation in cellulose upgrade scenarios

Electron beam irradiation (EBI) is an alternative treatment for intrinsic viscosity (IV) control in cellulose pulps, but has never been integrated in full bleaching sequences for comparison to conventional methods. Both eucalyptus kraft (EK) paper pulp and beech sulfite (BS) dissolving pulp were subjected to totally chlorine free (TCF) bleaching sequences comprising either EBI, ozone, or both for IV control. Additionally, effects of EBI on hexenuronic acid (HexA) and xylan were investigated. IV was adjusted to 450–500 mL g−1 and properties including carbonyl content, kappa, brightness, alkali-resistance and sugar composition were compared. Pulps produced with EBI had a higher alkali-resistance, uniformity and less cellulose oxidation. However, the degree of bleaching (DoB) was low without the use of ozone. HexA content in a birch pulp was halved by EBI. Isolated xylans were more resistant to irradiation than cellulose with little decrease of molar masses and moderate oxidation.

Effects of lignin chemistry on oxygen delignification performance

The present work focused on characterizing the chemical and structural properties of isolated lignin from six hardwoods and their kraft pulps in an attempt to better understand the relationship between lignin’s chemical properties and resultant oxygen delignification performance. Several hardwood samples were cooked under the same conditions with varying alkali charges to obtain unbleached pulps with kappa numbers between 19 and 20. These pulps were then subjected to an oxygen delignification stage. Both processes were evaluated for pulp quality, residual lignin, and O-stage delignification efficiency. The oxygen delignification stage was carried out under fixed conditions and evaluated with regards to kappa number, which was corrected for hexenuronic acid (HexA) contributions.Results revealed that different hardwood species exhibited differing oxygen delignification efficiencies. A high correlation was found between the O-stage delignification efficiency and the content of phenolic groups in the unbleached lignin, which confirmed that free phenolic groups are the reactive site for molecular oxygen attack. When different hardwood species were compared, the HexA contents were not found to affect O-stage delignification efficiencies.

SO2–ethanol–water (SEW) and kraft pulping of giant milkweed (Calotropis procera) for cellulose acetate film production

SO2–ethanol–water (SEW) fractionation and kraft pulping were applied to produce pulp from stem chips of Calotropis procera. The two pulps with different purities of cellulose were used for the production of cellulose acetate (CA) films. The motivation of this study was to investigate the possibility to produce high-quality cellulose CA films from low-grade pulp. The results showed that SEW pulping was more efficient in the selective removal of lignin and hemicelluloses from Calotropis procera wood as compared to kraft pulping. There, the pulping intensity was enhanced by increasing the H-factor to reach low lignin and hexenuronic acid (HexA) concentrations. However, a relatively high amount of alkali-insoluble xylan remained in the bleached kraft pulp and also the HexA content could not be fully removed during ECF-bleaching. In contrast, xylan was readily removed during SEW pulping and only a small amount of HexA (8.6 meq/kg) was observed in the pulp. High weight gains of about 55 and 63% were obtained during acetylation of kraft pulp and SEW pulp, respectively indicating a high degree of substitution (DS). The CA films prepared from both kraft and SEW pulps revealed higher transparency (88.0 and 88.5%), tensile stress (109 and 146 MPa) and modulus (4.6 and 5.6 GPa) as reported by previous studies. The results confirmed that CA films can be produced from SEW or kraft pulps through iodine catalysis showing similar properties than those obtained from high-purity dissolving pulps.

Xylanase Treatment Suppresses Light- and Heat-Induced Yellowing of Pulp.

Xylanase is commonly applied in pulp and paper industries to ease cost-related and environmental pressures. The effect of xylanase treatment on pulp bleaching is well-established, however, few studies were conducted on the effects of xylanase treatment in pulp yellowing, especially the mechanism of pulp yellowing inhibition by xylanase treatment. In this study, pure xylanase (EC 3.2.1.8) was applied to treat wheat straw chemical pulp (CP) and poplar chemi-thermo-mechanical pulp (CTMP) to determine their effects on pulp brightness and on light- and heat-induced yellowing. The xylanase treatment decreased the post-color number of the pulps during light- and heat-induced yellowing. However, differences were observed in the yellowing inhibition between the wheat straw CP and poplar CTMP. The changes in chemical components of pulps after the xylanase treatment, for example, lignin, hemicellulose, and HexA contents, and analysis of UV–vis absorption spectra and Fourier transform infrared-attenuated total reflectance spectrum were used to explore the pulp yellowing inhibition causes by the xylanase treatment.

EFEITOS DA XILANA NA PRODUÇÃO DE CELULOSE DE EUCALIPTO

RESUMO A busca por uma melhor utilização da madeira na indústria de celulose tem alimentado o interesse em uma utilização mais racional dos seus componentes, em particular as xilanas. O impacto da remoção das xilanas e de sua redeposição nas propriedades da polpa solúvel e tipos de papel de imprimir e escrever (P&W), são discutidos neste trabalho. Celulose kraft (15,6% xilanas) tratamento com 10-70 g.L-1 NaOH resultou em polpas de 14,5-5,9% de xilanas. Os tratamentos diminuiu a lignina e teores de HexA e causou impacto positivo significativo na deslignificação com oxigênio e posterior branqueamento ECF. A remoção de xilanas diminuiu a refinabilidade da polpa, índice de retenção de água e índice de tração, mas aumentou a drenabilidade, a capacidade de absorção de água, a capilaridade Klemm e o bulk. No geral, polpas com baixo teor de xilanas mostrou propriedades quase ideais de polpas para dissolução. Em uma segunda etapa da pesquisa, xilanas extraída de polpa não branqueada (BXL) e polpa de eucalipto branqueada (WXL) por extração cáustica fria (CCE) foram adicionados a uma polpa marrom comercial na deslignificação com oxigênio (O-estágio) e foi branqueada. Deposição de xilanas ocorreu em grau variável (até 7% em peso de celulose), dependendo do pH da reação do O-estágio. O branqueamento da polpa não foi prejudicada por WXL deposição de xilanas, mas ligeiramente afetada negativamente por xilanas BXL. A refinabilidade da polpa celulósica foi melhorada pela deposição de xilanas. As xilanas depositadas foram bastante estáveis ao longo do branqueamento, apesar de, com as xilanas WXL ser mais estável do que com as BXL. Em baixo consumo de energia, as xilanas depositados melhorou as propriedades física e mecânicas. A extração de xilanas pelo CCE com posterior deposição em polpa no O-estágio mostrou atraente para a fabricação de polpa com alto conteúdo de xilanas tipos de papel P&W.

Effects of D0-stage temperature, pH, and kappa factor on chlorine dioxide decomposition and D0-(EP)-D1 bleaching performance for eucalypt pulps

Mills have largely used chlorine dioxide (ClO2) for eucalyptus kraft pulp bleaching. Different mills have observed significant variation in ClO2 demand to reach full brightness (≥90 ISO). These large differences in ClO2 consumption derive from many factors. The most significant include differences in carryover loads and hexenuronic acid (HexA) contents and the level of chlorate formation across bleaching. Handling of pulp with high HexA content and ClO2 losses to chlorate can be minimized by proper operation of the ClO2 stages across the bleach plant. An oxygen delignified eucalyptus kraft pulp with a kappa of 10-12 units contains only 4-6 units actually derived from lignin. This scarce amount of lignin (0.6%-0.9%) is not able to consume high ClO2 doses and, as a consequence, the excess ClO2 applied can end up being converted into chlorate. Hence, proper optimization of ClO2 bleaching stages can save significant amounts of this oxidant. This study focused on optimizing ClO2 bleaching for a typical oxygen delignified eucalyptus kraft pulp of kappa number 11.7. Elemental chlorine free bleaching was carried out with the D0-(EP)-D1 sequence. The following conditions were varied in the D0 stage: temperature, end pH, and kappa factor. The results indicated that maximum ClO2 bleaching efficiency is achieved when minimum chlorate is formed, especially when ClO2 bleaching is adjusted in such a way that residual active chlorine is maintained to a minimum. The most significant variable affecting chlorate formation is pH; however, ClO2 doses (ClO2 concentration) also play a very important role. Chlorate formation is more intense in the D1 stage in relation to the D0 stage. Optimum conditions to run the D0 stage were 90°C, 3.5 pH, and 0.22 kappa factor.

Xylanase-Aided Chlorine Dioxide Bleaching of Bagasse Pulp to Reduce AOX Formation

Xylanase pretreatment was used to improve the chlorine dioxide bleaching of bagasse pulp. The pulp was pretreated with xylanase, which was followed by a chlorine dioxide bleaching stage. The HexA content of the pulp and the AOX content of the bleaching effluent were measured using UV-Vis and GC-MS methods, respectively. The results showed that a good correlation occurred between HexA and kappa number. HexA content of the pulp decreased significantly after the xylanase pretreatment. The AOX content of the bleaching effluent decreased as HexA was removed from the pulp. It was found that AOX could be reduced by up to 29.8%, comparing XD0 with a D0 stage. Fourier transform infrared spectroscopy (FTIR) was employed to determine the breakage of chemical bonds in the pulp. It revealed that some lignin and hemicellulose were removed after xylanase treatment. The GC-MS results showed that some toxic chloride such as 2,4,6-trichlorophenol could be completely removed after xylanase pretreatment.

Neutral Sulfite Treatment of Lignocellulosic Pulps

Birch and eucalyptus kraft pulps were treated with sulfite solutions in neutral conditions (pH 7) at 170 °C for 60 min and at 190 °C for 180 min. The pulps were analyzed for kappa number, viscosity, carbohydrate composition, and optical properties. Additionally, UV resonance Raman (UVRR) spectroscopy was applied to collect information on the contents of hexenuronic acid (HexA), lignin, and its phenolic hydroxyl groups. The sulfite treatments resulted in (i) depolymerization and partial dissolution of cellulose, (ii) partial dissolution of xylan and substantial decrease in its HexA content, and (iii) removal of the major part of lignin and increase in its phenolic hydroxyl group content. The extensive removal of HexA and depolymerization of cellulose by neutral sulfite were unexpected phenomena that have not been previously reported. According to their degree of polymerization (DP), the pulps were mainly in the form of microcrystalline cellulose after the more drastic treatments.

INFLUENCE OF XYLAN CONTENT ON THE OXYGEN DELIGNIFICATION PERFORMANCE OF EUCALYPT KRAFT PULPS AS STUDIED USING PREHYDROLYSIS AND XYLANASE TREATMENTS

Common metrics for evaluating the efficiency of oxygen delignification include the kappa number and Klason lignin content. As a change in xylan content often leads to a change in HexA content, the kappa number must be corrected for the HexA contribution before evaluating the degree of oxygen delignification when trying to understand the process in detail. Questions could also be raised about the accuracy of the Klason lignin method for oxygen-delignified hardwood kraft pulps, since the amount of residual lignin is small in such pulp. This study investigates the influence of xylan content on oxygen delignification efficiency in Eucalyptus urograndis kraft pulps. Xylan content was varied using two methods: treatment with xylanase and with acid prehydrolysis for various times before kraft cooking. The degree of oxygen delignification, expressed as the HexA-corrected kappa number, indicated no significant trend with xylan removal, and no significant trend was evident when expressed as Klason lignin content.

Antioxidant property of TCF pulp with a high hexenuronic acid (HexA) content

Abstract Totally chlorine free (TCF) pulp with a high content of hexenuronic acids (HexAs) was found to possess a high antioxidant power. The contribution of HexA to kappa number in unbleached Eucalyptus globulus kraft pulp was estimated to be 1.05 units per 10 μmol of HexA. The variation of HexA and lignin contents in enzymatic elemental chlorine free (ECF) and TCF sequences was monitored, and interesting effects were observed during the TCF XLE sequence, where X denotes an enzyme pretreatment with xylanase, L a laccase-mediator stage, and E an alkaline extraction stage. Thus, HexA removal during L stage was strongly enhanced after the X stage; also, the HexA content was decreased by the alkaline stage. None of these effects was observed in the ECF sequence with chlorine dioxide. The antioxidant power detected in HexA makes TCF pulp an excellent raw material for manufacturing packaging for easily oxidized products.

Development of a novel empirical model to estimate the kraft pulp yield of fast-growing Eucalyptus

In this study, several kraft pulps were produced by kraft pulping of fast-growing Eucalyptus with a wide range of cooking conditions. The dependences between pulp yields and some pulp properties, namely, kappa number, HexA contents, and cellulose viscosities, were well investigated. It was found that kraft pulp yields linearly decreased with the reduction of HexA-free kappa number in two different stages, respectively, in which a transition point of measured pulp yield of 48.7% was observed. A similar relationship between pulp yield and HexA was also found, in which the resulting transition point of HexA content was 67 μmol/g. Moreover, the logarithm of pulp viscosity was linearly proportional to the reduction of lignin-free pulp yields. Then, a novel empirical model was successfully developed based on these findings. The parameters in this empirical model were calculated by least-squares estimation using the experimental data from active alkali values of 13.2, 14.7 and 17.8. Another data set was used to verify the effectiveness of this model in predicting the pulp yields. Finally, a good agreement (a linear regression coefficient of 90.59%) between experimental and fitting data was obtained, which indicated that the kraft pulp yield of fast-growing Eucalyptus could be accurately predicted by this novel empirical model.

Differential behavior between acacia and Japanese larch woods in the formation and decomposition of hexenuronic acid during alkaline cooking

The effects of anthraquinone (AQ) and polysulfide (PS) on the hexenuronic acid (HexA) content of pulp during kraft cooking were studied using Acacia mearnsii (acacia) and Larix leptolepis (Japanese larch) sapwood. In contrast to the results of cooking Japanese larch at an H-factor of 1200, the HexA contents of acacia pulp with a kappa number of 20 at an H-factor of 291 did not differ greatly between the kraft, kraft-AQ, and PS-AQ cooking methods, although the hydroxide ion concentration in the acacia cooking liquor decreased on the addition of AQ or sulfur. To explain this difference, we studied the behavior of the formation and degradation of HexA during alkaline cooking of glucuronoxylan from cotton linter, which was cooked with 1.0 and 2.0 mol/l NaOH. The relationship between HexA content and H-factor during alkaline cooking of glucuronoxylan was clarified. The amount of HexA and its rate of decomposition were higher in the 2.0 mol/l solution than in the 1.0 mol/l solution. At a low H-factor similar to that for hardwood cooking, HexA content increased to a maximum level and then started to decrease at high hydroxide ion concentrations such as 2.0 mol/l, whereas it slowly decreased at low hydroxide concentrations such as 1.0 mol/l. At an H-factor of around 450, the HexA formation/degradation curve for 1.0 mol/l of hydroxide crossed the decomposition curve for 2.0 mol/l of hydroxide. Therefore, it was shown that at a low H-factor, a decrease in hydroxide ion concentration during acacia wood cooking had little effect on the HexA content of pulp.

Xylanase- and laccase-aided hexenuronic acids and lignin removal from specialty sisal fibres

This work was conceived to investigate for the first time the effectiveness of the combined use of xylanase and laccase for the removal of hexenuronic acids (HexA) and lignin from sisal pulp fibres. To this end, xylanase (X) and laccase (L) treatments were used in an XLQPo sequence (where Q denotes a chelating stage and Po an oxygen-reinforced peroxide multi-step treatment) that was applied to pulp in order to obtain sisal fibres with a high cellulose content. The results of the XLQPo sequence were compared with those of an LQPo sequence. The L stage of both sequences was performed in the presence of either the natural compound sinapyl aldehyde (SLD) or the synthetic compound violuric acid (VA), employed as mediators, in order to compare their efficiency in aiding pulp bleaching and HexA removal. Changes in HexA content and the contributions of lignin and HexA to kappa number during each sequence were examined. The xylanase treatment was found to remove 47% of lignin, 15% of xylan and 27% of HexA from the initial pulp, whereas the laccase–VA system removed 28% of HexA and exhibited higher efficiency than the laccase–SLD system in reducing kappa number and increasing brightness. In any case, when the X treatment was applied, the sequence including laccase–SLD treatment resulted in the strongest delignification effect. The effluents from each stage of the bleaching sequences were analysed for COD, colour and toxicity, which peaked after the L stage and were significantly higher with SLD than with VA.

Performance of new and commercial xylanases for ECF and TCF bleaching of eucalyptus kraft pulp

Since xylanases can differ widely in their bleaching efficiency, the performance of one new and two commercial xylanases was evaluated in an eucalyptus kraft pulp following XD (X: xylanase; D: chlorine dioxide) and XP (P: hydrogen peroxide) sequences. The new xylanase did not show a significant bleach boosting effect but increased the hexenuronic acid (HexA) removal by 10% after the D stage. The two commercial xylanases behaved in a different way, being one of them (XC) the most effective in increasing delignification (9%) and brightness (3%ISO). Its effectiveness was related to its greater action on releasing the xylan polymer, thus producing also a strong decrease in the HexA contents during the enzymatic stage (15%). All xylanases produced morphological changes in the fibre surfaces, but only with XC cracks and holes that improved the diffusion of reactives were observed. Finally, the best bleaching results were obtained with the XD sequence and therefore, a complete bleaching sequence XDEopD1 (Eop: alkaline extraction with oxygen and peroxide) was carried out with the best enzyme.

Simulating the impact of kraft pulping and bleaching parameters on Eucalyptus camaldulensis pulp properties using MATLAB

AbstractIn this work, Eucalyptus camaldulensis was evaluated as the raw material for chemical pulp under different pulping and bleaching conditions. The pulping was carried out at different H‐factors, and at different effective alkalis. The resulting pulps were then oxygen delignified and bleached using various dosages of bleaching chemicals in a D0EpD1 sequence. The effect of independent variables (pulping or bleaching variables) on dependent variables (pulp properties) was analysed based on the multivariable least square method via MATLAB software. An agreement was found between the results predicted from the models and the experimental data. To obtain a kappa number of 15, the optimum pulping conditions were a temperature of 155°C, a time of 225 min, and an EA of 23%. Also, the hexenuronic acid (HexA) content of cooked pulp was significantly decreased in the chlorine dioxide bleaching stages, and was only marginally related to the final HexA content of bleached pulps.

Effect of last stage bleaching with peracetic acid on brightness development and properties of eucalyptus pulp

Investigation of last stage bleaching with peracetic acid is the main subject of this paper. Proper conditions were established to apply peracetic acid as the last bleaching stage of the D(Ep)D/Paa, DHT(Ep)D/Paa, A/D(Ep)D/Paa, DHT/Q(PO)Paa and Z/ED/Paa sequences. In addition, the impact of last stage bleaching with Paa on pulp refinability and strength properties was determined. Peracetic acid was consumed relatively fast when applied as the last stage of ECF bleaching sequences. A reaction time of 120 min at 75 oC and pH 5.0 is seemingly adequate regardless of the Paa dose, in the range of 1-5 kg/odt pulp and bleaching sequence. The optimum dose of Paa depends upon the sequence under investigation. In general the Paa application as last bleaching stage caused slight decrease in pulp viscosity, kappa number and HexA content but had no significant effect on pulp reversion and L*a*b* coordinates. The refinability and bonding strength properties of the pulps bleached with the sequences DHT(Ep)DD and DHT(Ep)D/Paa were quite similar when the pH of the last bleaching stage of both sequences were near 5. These properties improved slightly when Paa bleaching pH was raised to 8.5.

Obtaining low-HexA-content cellulose from eucalypt fibres: Which glycosil hydrolase family is more efficient?

Four new bacterial xylanases from different glycosyl hydrolase families (11, 10 and 5) were evaluated for hexenuronic acid (HexA) removal capacity and bleach boosting ability of a eucalypt kraft pulp. The family 11 xylanase was the most effective in enhancing HexA removal and also in increasing delignification and brightness. A very innovative point was that a xylanase from family 5 was applied in pulp bleaching for the first time, showing a notable contribution to pulp bleachability. On the contrary, the family 10 xylanases did not modify kappa number or brightness. A remarkable effect was that the tested xylanases reduced pulp HexA content. The effects produced by the different xylanases in pulp properties were closely related with the effects observed in the effluent properties. The effluents from enzymatic treatments showed the dissolved xylans and xylooligosaccharides branched with HexA, as well as lignin. In addition, a simple tool to assess the boost bleaching ability of a xylanase treatment was also used.

The role of xylanases and laccases on hexenuronic acid and lignin removal

The variation of the contents in hexenuronic acids (HexA) and lignin in eucalyptus kraft pulp during sequences with the laccase–mediator treatment with or without xylanase pretreatment was studied. The laccase–HBT system (HBT: 1-hydroxybenzotriazole) initially oxidized lignin alone but altered cellulose in the pulp as well after some time. Once all accessible lignin was removed, the system acted on HexA. As a result, the laccase–mediator treatment reduced the HexA content of the pulp, especially if a xylanase pretreatment was applied before. A previously unseen effect was observed here: HexA removal was found to depend on the laccase and HBT doses, but not on the reaction time. In addition, the xylanase pretreatment was found to strongly boost the effects of the laccase–HBT system by facilitating their access to HexA without affecting the lignin content.