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Sulfur makeup in an unbleached kraft pulp mill, TAPPI Journal August 2024
ABSTRACT: Sodium sesquisulfate or “sesqui” (Na3H(SO4)2) is a by-product of chlorine dioxide production at kraft pulp mills. It is typically used for sodium and sulfur makeup in the liquor loop. Mondi Hinton Inc. (MHI) in Hinton, AB, Canada, was converting from bleached to unbleached kraft pulp production and was thus losing this source of makeup. The only option that was readily available as a substitute was sodium hydrosulfide (NaHS), which was cost prohibitive. Other options such as sodium sulfate (Na2SO4), emulsified sulfur, sulfuric acid (H2SO4), and sodium bisulfite (NaHSO3) were compared. The mill concluded that pelletized sulfur plus sodium hydroxide or “caustic soda” (NaOH) was the best option. Laboratory-scale experiments showed that pelletized sulfur dissolved in white liquor (WL). A mill-scale trial revealed that pelletized sulfur added to a causticizer had no adverse impacts on the downstream pressure filters or kiln operation. The sulfur reacted to produce polysulfide upstream of the WL storage tank, giving the liquor an orange hue. This polysulfide appeared to partially degrade into thiosulfate before being fed to the digester. The heavy black liquor (HBL) sulfur:sodium (S:Na) ratio did not change significantly, even though the sulfur/soda addition location was upstream of the original one. In addition, other properties such as liquor heating value and elemental analysis did not significantly change. Due to polysulfide/thiosulfate concentration in the white liquor, it was determined that the carbon steel equipment was at risk for corrosion. During the annual turnaround that occurred eight months after the addition of sulfur was started, the wash zone of the digester showed no signs of thinning/damage. The mill has been running exclusively with pelletized sulfur for 22 months (as of August 2024), realizing significant cost savings compared to the use of NaHS or other sulfur/soda addition options.
Journal articles
Magazine articles
The role of hornification in the deterioration mechanism of physical properties of unrefined eucalyptus fibers during paper recycling, TAPPI Journal February 2024
ABSTRACT: Physical properties of cellulosic paper deteriorate significantly during paper recycling, which hinders the sustainable development of the paper industry. This work investigates the property deterioration mechanism and the role of hornification in the recycling process of unrefined eucalyptus fibers. The results showed that during the recycling process, the hornification gradually deepened, the fiber width gradually decreased, and the physical properties of the paper also gradually decreased. After five cycles of reuse, the relative bonding area decreased by 17.6%, while the relative bonding force decreased by 1.8%. Further results indicated that the physical property deterioration of the paper was closely related to the decrease of fiber bonding area. The fiber bonding area decreased linearly with the reduction of re-swollen fiber width during paper recycling. Re-swollen fiber width was closely related to the hornification. Hornification mainly reduces the bonding area of unrefined eucalyptus fiber rather than the bonding force. The work elucidates the role of hornification in the recycling process of unrefined eucalyptus fibers and the deterioration mechanism of paper physical properties, which will be helpful to control the property deterioration of paper and achieve a longer life cycle.
Journal articles
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Effects of different soda loss measurement techniques on brownstock quality, TAPPI Journal July 2024
ABSTRACT: The efficiency of the kraft recovery plant, bleaching process, and paper machine are affected when black liquor carryover from the brownstock washers is not controlled well. Measuring soda loss within a mill can vary from using conductivity, either in-situ or with a lab sample of black liquor filtrate squeezed from the last stage washer, to measuring absolute sodium content with a lab sodium specific ion probe or spectrophotometer. While measuring conductivity has value in tracking trends in black liquor losses, it is not an acceptable method in reporting losses in absolute units, typically in lb/ton of pulp. This is further complicated when trying to benchmark soda loss performance across a fleet of mills with multiple washer lines. Not only do the testing methods vary, but the amount of bound soda on high kappa pulps can be significant. This variability creates inconsistent results, and studies are needed to understand the effect of different testing methods on the pulp quality. In this study, soda loss is expressed as sodium sulfate (Na2SO4). Four different methods to measure soda content in pulp off commercial brownstock washers were studied: full digestion (FD), washing soaking overnight and washing (WSW), soaking in boiling water and stirring 10-min (SW-10), and squeeze-no wash (Sq). Total, washable, and bound sodium sulfate calculations were determined for each soda content measuring technique using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Results showed bound and washable sodium sulfate amounts significantly depend on which soda measurement technique was used. In addition, the soda results were correlated with the pulp kappa numbers. As the kappa number increases, bound soda increases, regardless of the soda measurement method used. Impacts of high sodium sulfate in brownstock are also discussed.
Journal articles
Biomass gasification for green ammonia production in kraft mills, TAPPI Journal September 2026
ABSTRACT: As the global energy sector transitions toward net-zero emissions, kraft pulp mills present a compelling opportunity to produce green fuels and achieve net-negative emissions by capturing biogenic carbon, helping offset hard-to-abate sectors. This study explores the techno-economics of integrating biomass gasification for green ammonia production within kraft mills, using KraftSIM modeling to evaluate ammonia production, steam balance, emissions, and utility impacts. The proposed design enables energy and water system integration with the existing mill and allows for a gradual scale-up without disrupting the chemistry and operation of the recovery cycle. Across five scenarios representing different biomass gasification rates ranging from 100 to 1000 bone-dry metric tons per day (BDMT/d), the process yields ammonia at approximately 0.51 metric tons per bone-dry metric ton (t/ BDMT), while generating significant low- and medium-pressure steam and hot water that offset mill utility demands. The incineration of pressure swing adsorption tail gas and ammonia plant purge gas in the power boiler reduces biomass combustion and enhances power boiler efficiency. Economic analysis suggests a net revenue potential of approximately CA$380/BDMT, which could increase with the implementation of biogenic carbon pricing. Overall profitability is strongly influenced by biomass procurement costs, electricity prices, and prevailing green fuel and chemical market premium. This work outlines a practical, near-term decarbonization pathway for kraft mills by coupling green fuel production with potential opportunities for carbon removal.
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Influence of tensile straining and fibril angle on the stiffness and strength of previously dried kraft pulp fibers, TAPPI JOURNAL July 2018
Influence of tensile straining and fibril angle on the stiffness and strength of previously dried kraft pulp fibers, TAPPI JOURNAL July 2018
Journal articles
Magazine articles
Fundamental molecular characterization and comparison of the O, D0, and E stage effluents from hardwood pulp bleaching, TAPPI Journal 2019
ABSTRACT: The present study characterized effluents from the O, D0, and E stages using nuclear magnetic reso-nance (NMR) and gel permeation chromatography (GPC) techniques to better understand the chemical nature of the dissolved organics formed from the bleaching of a high-yield hardwood kraft pulp. Understanding the structures and molecular weight distribution of these organics is the first step in developing methods to mitigate these contam-inates in the discharged effluents. The results indicated that the molecular weight distribution (MWD) of the dis-solved organics from oxygen delignification effluent is broader than those from D0 and E stage effluents. In addition, the O stage filtrate contained considerable amounts of lignin and xylan fragments, which showed its efficiency in removing such materials. The effluent from the D0 stage contained a lower amount of high molecular weight frag-ments and a higher amount of low molecular weight fragments versus the O-stage filtrate. Aromatic structures were nearly absent in the D0 stage filtrate, but the degraded organic material, presumably from oxidized lignin, contained olefinic (C=C) and carbonyl (C=O) functional groups. Furthermore, higher molecular weight fragments were detected in the E-stage effluent, presumably due to the extensive solubilization and removal of the oxidized lignin generated from the D0 pulp.
Journal articles
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In-situ green synthesis and adsorption on methylene blue of copper-based metal organic framework/cellulose/chitosan (CCTSA/HKUST-1) composite aerogel, TAPPI Journal October 2024
ABSTRACT: In order to explore the application of metal-organic frameworks (MOFs) in environmental and water treatment fields, a new composite aerogel of HKUST-1/cellulose/chitosan (CCTSA/HKUST-1) with better hydrostability was synthesized by an in-situ synthesis method combining covalent cross-linking and solvothermal methods as an efficient adsorbent for methylene blue (MB). The composite aerogel (CCTSA) obtained by covalent cross-linking of cellulose (CE) and chitosan (CTS) exhibited excellent stability under strong acid and solvent-thermal conditions. With the increase of CTS content, it was beneficial to the in-situ synthesis of HKUST-1, as well as to increase the mass loading rate of HKUST-1 to 37.06%, while the Brunauer-Emmett-Teller (BET) specific surface area of CCTSA/HKUST-1 composite aerogel reached 945.123 m2·g-1, which was much higher than that of the CCTSA composite aerogel (14.489 m2·g-1). The CCTSA/ HKUST-1 composite aerogel exhibited excellent adsorption capacity (537.6 mg·g-1) on MB solution, and cyclic adsorption could be achieved. This study proposes a concept of valorization of alkaline peroxide mechanical pulping (APMP) waste liquor to hemicellulose-based hydrogel. This hemicellulose-based hydrogel exhibits a sensitive temperature/pH dual response. Hemicellulose-based hydrogels swell or shrink through the change of hydrogen bond/electrostatic repulsion/charge screening. They also show good water absorption and water retention properties.
Journal articles
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CFD and predictive modeling of temperature and calcination in a rotary lime kiln • Potential for steadier kiln operation, TAPPI Journal October 2024
ABSTRACT: Rotary lime kilns are used in the pulp and paper industry to calcine lime mud to lime. Lime kiln models provide a means to understand the complex phenomena occurring within the kiln to aid in problem-solving during operation. A two-dimensional (2D) computational fluid dynamics (CFD) and one-dimensional (1D) bed model was previously developed for steady-state and transient analysis. This study explores data extracted from the model over a longer time period. The simulated outlet gas and shell temperature are compared to measured data for validation. The capability of using the model to estimate the production rate, accounting for the residence time within the kiln, is discussed. The maximum refractory wall temperature is analyzed during operation. Fluctuations in the calcination location are compared to outer shell heat-map data to correlate the calcination location and ring formation and growth. The model results to date indicate that fluctuations in the calcination zone may contribute to problematic ring growth, though a direct correlation has yet to be established. Additionally, a method for steadier kiln control is introduced and discussed. A machine learning model is also developed to predict the calcination start location from industrial data and is compared to the CFD model for validation. This model can generate results quickly and without the need for knowledge in CFD software and theory. Good agreement is found between the CFD and machine learning model during operation, with a mean absolute error (MAE) of 0.46 m, a mean absolute percentage error (MAPE) of 0.92%, and a root mean square error (RMSE) of 1.17 m.
Journal articles
Magazine articles
Biofuels in lime kilns • Operating experience in the Nordic pulp and paper industry, TAPPI Journal October 2024
ABSTRACT: The lime reburning process is a central part of the chemical pulp mill. It is energy intensive and consumes large amounts of fossil fuel, globally consuming about 50 terawatt-hours (TWh) of fuel per year. Conversion to operation with biofuel is interesting, both to reduce carbon dioxide emissions and to reduce costs. Researchers interviewed managers in mills that use solid, liquid, or gasified biofuels to replace fuel oil or natural gas in their lime kilns, and they conducted surveys related to fuel consumption and operations and maintenance. In Sweden and Finland, there were ten mills in 2020 using biomass powder or gasified biomass as the primary fuel, and two more installations were under construction. There were also nine installations in operation or under construction outside the Nordic countries. Fourteen mills in Sweden and two mills in Finland used tall oil pitch as the main fuel. Fuel consumption in Swedish lime kilns was 3.8 TWh in 2020, and 90% of this energy was supplied with biofuels. Of about 4.2 TWh used in Finnish lime kilns, approximately 45% was supplied with biofuels. Developments in the design of the fuel supply system include belt dryers being used in all new installations and mass flow metered dosing systems being used in most new pulverized fuel installations. Bark gasifiers have increased considerably in size. Lignin powder firing has been established as a proven option. A solution for many Swedish and Finnish mills is the use of tall oil pitch as a replacement for fuel oil.
Journal articles
Magazine articles
Model development for real oxygen delignification processes, TAPPI Journal October 2024
ABSTRACT: Previous extensive work has been done on modeling the oxygen delignification process, based on how the basic parameters, i.e., temperature, kappa number, concentration of alkali, and concentration of oxygen, affect the delignification rate. However, these models are not used extensively to evaluate the performance of real processes, primarily because they have not been able to properly consider all the essential issues affecting delignification in practice. Such issues include the mass transfer and consumption of oxygen, which defines the concentration of dissolved oxygen in the process, and the effect of that concentration on the delignification rate. In this paper, a new way to model the oxygen delignification process is used in which these parameters, among other smaller matters, are taken into account. The basic model and its parameters were defined by the information obtained from the literature, delignification made in the laboratory tests, and mill processes and mill tests. An essential aspect of these studies was the information obtained from the oxygen concentration measured in the residual gas obtained from the top of the reactor. With the aid of this measurement, it was possible to define more accurately the consumption of oxygen and partial pressure of oxygen that define the concentration of dissolved oxygen in the reactor. Using mill experiments, a model was formed that predicts the operation of the oxygen delignification process. The model was used to show how much the process could be improved by optimizing the charge of the oxygen. The mill experiments also confirmed that mass transfer of oxygen is modeled correctly enough, except when the charge of oxygen is very low and/or the mixing is not efficient enough. In that case, there is variation in the concentration of oxygen in the process that should be taken into account in the modeling.