Technological evaluation of Pinus maximinoi wood for industrial use in kraft pulp production

This study characterized Pinus maximinoi wood and evaluated its performance for pulp production. Samples of Pinus taeda wood were used as reference material. For both species, wood chips from 14-year-old trees were used for the technological characterization, pulping, bleaching process analysis, and pulp properties. A modified kraft pulping process was carried out targeting kappa number 28±5% on brownstock pulp. The bleaching sequence was applied for bleached pulp with final brightness of 87±1 % ISO. Refinability and resistance properties were measured in the bleached pulps. Compared to P. taeda wood, P. maximinoi showed slightly higher basic density (0.399 g/cm³) and higher holocellulose (64.5%), lignin (31.1%), and extractives content (4.5%), along with lower ash content (0.16%). P. maximinoi tracheids showed greater wall thickness (6.4 µm) when compared to P. taeda tracheids. For the same kappa number, P. maximinoi and P. taeda resulted in similar screened yield, with an advantage observed for P. maximinoi, which resulted in lower specific wood consumption (5.281 m³/o.d. metric ton), and lower black liquor solids (1.613 metric tons/o.d. metric ton). After oxygen delignification, P. maximinoi pulp showed higher efficiency on kappa reduction (67.2%) and similar bleaching chemical demand as P. taeda pulp. Compared to P. taeda pulps, the refined P. maximinoi pulps had similar results and the bulk property was 10% higher. Results showed that P. maximinoi is an interesting alternative raw material for softwood pulp production in Brazil.

Bleaching of bagasse-pulp using short TCF and ECF sequence

More than 70 % bleached chemical pulp is produced in India through elemental chlorine-free bleaching in which chlorine-based compounds like chlorine dioxide is a dominant chemical which generates chlorinated organic toxins harmful to the environment. Present studies demonstrate short sequence of bleaching combined with acid treatment, followed by pressurized oxygen delignification. It was found that efficiency of oxygen improved by adding hydrogen peroxide as an additive in oxygen delignification with subsequent treatment with ozone or chlorine dioxide as bleaching agents. It was observed that by using additive in ODL process, pulp can achieve 70±1 (%ISO) brightness. Reduction attains in kappa number 65–70 % as compared to 45–50 % in control oxygen delignification stage. Through AOpZ and AOpD bleaching sequences, full brightness achieved 84–85 (%ISO) without considerable loss in mechanical strength properties compared to DEpD sequence. A potential reduction in COD, color, and AOX was 28, 53.3, and 88 % respectively were observed in AOpZ short bleaching sequence compared to DEpD bleaching.

Gas dispersion in the oxygen delignification process

There has been very little knowledge about the state of gas dispersion in the oxygen delignification process, even though this has a major impact on the performance of the reactor. This paper presents a new continu-ous inline method for measuring oxygen bubble size distribution in the reactor, as well as results from studies con-ducted in softwood and hardwood lines. This new measurement worked well, and new information about oxygen bubble size, as well as how different reactor conditions affected the distribution, was obtained. For example: • In the softwood line, the mean volume-weighted bubble size was about 0.1 mm, whereas in the hardwood line, this size was almost 10 times higher. For both lines, there was considerable variation in the measured bubble size over the long term. • For both lines, an increase in mixer rotation speed caused a discernible decrease in the bubble size, and an increase in oxygen charge caused a discernible increase in the bubble size. • In the softwood line, no coalescence of the bubbles in the reactor was observed, but in the hardwood line, some coalescence of the larger bubbles occurred. • In the test conducted in the hardwood line, the use of brownstock washer defoamer caused a discernible increase in oxygen bubble size. • In the hardwood line, reactor pressure had a noticeable effect on the amount of delignification, which indicated that improving mass transfer of oxygen (e.g., by decreasing the oxygen bubble size, in this case) should also have an increasing effect on the delignification.

The role of gas dispersion in the oxygen delignification process

Oxygen delignification is an essential part of the pulp production process. Delignification occurs with the aid of alkali and dissolved oxygen. Dissolved oxygen is obtained by dispersing oxygen gas into the pulp suspension by using efficient mixers. Little is known about the state of oxygen gas dispersion and its effect on oxy-gen delignification kinetics and efficiency. This paper will present the results for the effect of gas bubble size on the performance of oxygen delignification. The results are mainly based on detailed studies made in a Finnish hardwood mill where the oxygen bubble size distribution could be altered at the feed of the reactor. An essential aspect of these studies was the use of a new continuous inline gas bubble size measurement system to simultaneously determine the bubble size distribution at the feed and top of the reactor. Information about oxygen consumption in the reactor could also be obtained through the bubble size measurements. Accordingly, these studies quantify the effect of oxygen bubble size on the kappa reduction of the pulp. The effect of different chemical factors on the oxygen bubble size is also studied. Finally, the relationship between the gas bubble size and the liquid phase oxygen mass transfer coefficient (kLa) is presented. This connects the bubble size to the kappa reduction rate. Based on the presented modeling approach and the evaluation of practical factors that are not taken into account in the modeling, it was concluded that the volumetric average oxygen bubble size should preferably be smaller than 0.2 mm in practice. The information obtained with the new gas bubble size measurement system and the presented modeling approach give a very new basis for understanding, monitoring, adjusting, and designing oxygen delignification processes.

The Dual Effect of Ionic Liquid Pretreatment on the Eucalyptus Kraft Pulp during Oxygen Delignification Process

Oxygen delignification presents high efficiency but causes damage to cellulose, therefore leading to an undesired loss in pulp strength. The effect of ionic liquid pretreatment of [BMIM][HSO4] and [TEA][HSO4] on oxygen delignification of the eucalyptus kraft pulp was investigated at 10% IL loading and 10% pulp consistency, after which composition analysis, pulp and fiber characterizations, and the mechanism of lignin degradation were carried out. A possible dual effect of enhancing delignification and protecting fibers from oxidation damage occurred simultaneously. The proposed [TEA][HSO4] pretreatment facilitated lignin removal in oxygen delignification and provided fibers with improved DP, fiber length and width, and curl index, resulting in the enhanced physical strength of pulp. Particularly, its folding endurance improved by 110%. An unusual brightness reduction was identified, followed by detailed characterization on the pulps and extracted lignin with FTIR, UV, XPS, and HSQC. It was proposed that [TEA][HSO4] catalyzed the cleavage of β-O-4 bonds in lignin during the oxygen delignification, with the formation of Hibbert’s ketones and quinonoid compounds. The decomposed lignin dissolved and migrated to the fiber surface, where they facilitated the access of the oxidation agent and protected the fiber framework from oxidation damage. Therefore, it was concluded that ionic liquid pretreatment has a dual effect on oxygen delignification.

Differences and similarities between kraft and oxygen delignification of softwood fibers: effects on mechanical properties

Charged groups in pulp have been shown to enhance the tensile strength of the paper produced from the pulp. Oxygen delignification introduces charged groups and it is of interest to determine how the delignification should be distributed between the cooking and the oxygen stage with respect to mechanical properties. A number of unbleached kraft cooked and oxygen delignified pulps within a wide kappa number range were produced and refined, and the effects of the refining on the morphology and mechanical properties were studied. The WRV correlated with the fiber charge and at a given fiber charge, kraft cooked and oxygen delignified pulps had the same WRV development in refining, although they had significantly different kappa numbers. The tensile strength development during refining depends on the fiber rigidity which is affected by the lignin content, the fiber charge and the chemical and mechanical processes used. Refining increased the curl of the kraft cooked pulps and decreased the curl of oxygen delignified pulps, irrespective of kappa number. A greater increase in tensile strength was seen for the pulps with a higher fiber charge and WRV, probably because of the greater degree of fibrillation achieved in the beating process. Despite the greater fiber deformation in the oxygen delignified pulps, the strength can be increased by a larger amount of charged groups and a greater swelling of the fibers. Graphic abstract

Differences and similarities between kraft and oxygen delignification of softwood fibers: effects on chemical and physical properties

The fiber properties after oxygen delignification and kraft pulping were studied by looking into the chemical characteristics and morphology. The effect of the two processes on the fibers was evaluated and compared over a wider kappa number range (from 62 down to15). Wide-angle X-ray scattering, nuclear magnetic resonance and fiber saturation point were used to characterize the fiber network structure. Fiber morphology and fiber dislocations were evaluated by an optical image analysis. The total and surface fiber charges were studied by conductometric and polyelectrolyte titrations. The fiber wall supramolecular structure, such as crystallinity, size of fibril aggregates, pore size and pore volume, were similar for the two processes. The selectivity, in terms of carbohydrate yield, was equal for kraft cooking and oxygen delignification, but the selectivity in terms of viscosity loss per amount of delignification is poorer for oxygen delignification. Clearly more fiber deformations (2–6% units in curl index) in the fibers after oxygen delignification were seen. Introduction of curl depended on the physical state of the fibers, i.e. liberated or in wood matrix. In the pulping stage, the fiber continue to be supported by neighboring fibers, as the delignified chips maintain their form. However, in the subsequent oxygen stage the fibers enter in the form of pulp (liberated fibers), which makes them more susceptible to changes in fiber form. Graphic abstract

Limitations on the protective action of MgSO4 for cellulose during kraft pulp oxygen delignification

Magnesium sulfate (MgSO4) is the most widely used protector for alleviating the effects that metal ions have on cellulose degradation. However, the efficiency of MgSO4 is limited by the oxygen delignification conditions. This work discusses the factors influencing MgSO4 efficiency in terms of cellulose protection and delignification. The type and concentration of metal ions, delignification rate, additions order, and mixing degree of MgSO4 should affect the cellulose degradation during oxygen delignification in the presence of MgSO4. The most adverse effects on cellulose are observed with Mn2+ and Fe2+ ions followed by Cu2+ and Fe3+. MgSO4 addition can diminish such negative effects; however the protection becomes reduced in the presence of higher concentrations of metal ions. In addition, the optimum MgSO4 application level is closely dependent on the delignification rate and metal ions concentration. Adding MgSO4 is optional for pulps with trace metal ions at relatively low delignification levels, but it is essential for pulps with concentrated metal ions or when the oxygen delignification rate is relatively high. More simply, when the added MgSO4 is thoroughly mixed with the pulp before the addition of NaOH, it exhibits a prominent effect on cellulose protection.