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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.
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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.
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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.
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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.
Journal articles
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Colloid chemical aspects of paper formation in the presence of nanofibrillated cellulose and cationic starch, TAPPI Journal September 2024
ABSTRACT: A series of experimental tests were carried out to examine colloidal-scale consequences of optionally treating nanofibrillated cellulose (NFC) with cationic starches of different charge density and dosage (0.5% or 2.0% by weight), adding that material to a furnish prepared from 100% recycled copy paper, and then subjecting the mixture to very different levels of hydrodynamic shear. Tests included optical microscopy, sediment volume tests, sediment velocity tests, and “percent fines” assessment by means of a fiber quality analyzer (FQA). In addition, the zeta potential and charge demand of the studied materials were evaluated. Optical imaging revealed that cationic starch treatment of the NFC tended to agglomerate it into multiparticle clusters, which sometimes could be mostly redispersed by hydrodynamic shear. Subsequent addition of the starch-treated NFC to the default furnish resulted in much of the colloidal material becoming attached to fibers. Subsequent shearing of the mixtures was at least partly effective in separating the clusters of NFC from the fiber surface, resulting in essentially a two-component mixture. Multiparticle NFC clusters coexisted with the fiber suspension, sometimes attached and sometimes not, depending on the details of treatments. Sediment volume tests showed that systems containing cationic starch-treated NFC tended to have a higher density after settling in comparison to untreated NFC; these findings are consistent with the cationic starch acting as a stabilizer on the solid surfaces, allowing them to slide past each other during the settling process. Application of intense hydrodynamic shear tended to result in denser sediment. Results of tests with the sediment velocity messurement and the FQA percent fines assessment did not correlate well with changes in test conditions considered in this study.
Journal articles
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PEERS 2023 Poster Session: a competition for students and young professionals, TAPPI Journal April 2023
ABTRACT: Originating in the field of scientific research and academia, poster sessions at conferences may date back to the mid-20th century, although the origins aren’t quite clear. Some sources have said as early as the 1950s and others later, while the term “poster session” itself may not have been coined until the 1975 American Physics Conference. The original concept behind poster sessions was to provide a platform for researchers to share their work in a more visual and interactive format as compared to the traditional long-form oral presentation.
Journal articles
Magazine articles
Black liquor evaporators upgrade — How many effects?, TAPPI Journal April 2023
ABSTRACT: Black liquor evaporation is generally the most energy intensive unit operation in a pulp and paper manufacturing facility. The black liquor evaporators can represent a third or more of the total mill steam usage, followed by the paper machine and digester. When considering an evaporator rebuild or a new system, the key design question is how many effects to include in the system. The number of effects is the main design feature that deter-mines the economy of the system and the steam usage for a given evaporation capacity. A higher number of effects increases steam economy and reduces energy cost to a point, but additional effects also have higher initial capital cost and increased power costs. This research paper uses life-cycle cost analysis (LCCA) as a method to determine the optimum number of evaporator effects for a new evaporator system. The same basic principles and method can also apply to existing evaporator rebuild projects.
Journal articles
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Dynamic CFD modeling of calcination in a rotary lime kiln with an external dryer, TAPPI Journal August 2023
ABSTRACT: Mid-kiln ring formation is a problem in lime kilns that may be related to fluctuations in the start location of calcination. To calculate fluctuations in bed and gas temperature profiles within a lime kiln with an external dryer, a dynamic two-dimensional (2D) axisymmetric computational fluid dynamics (CFD) gas model with a methane burner implemented in ANSYS Fluent, coupled by mass and heat balances to a one-dimensional (1D) bed model, was developed. The dynamic model was used to calculate changes in the location where calcination starts with fluctuations in operational conditions using pulp mill data. This model simulates radiative, convective, and conductive heat transfer between the gas, wall, and bed to determine the axial bed temperature in the kiln. The calcination reaction is described using a shrinking core model that allows for the prediction of the location at which calcination begins and the degree of calcination achieved. The solid motion within the kiln is modeled using Kramer’s equation modified for transient response. Steady-state and dynamic simulation results were compared to data from an industrial dry lime kiln, and good agreement was found. A sensitivity analysis was also performed to provide insight on how operating conditions and model variables impact the calcination location and degree of calcination. Of the variables examined, the fuel rate and the feed temperature had the largest impact on both the calcination location and degree of calcination in the kiln. Model predictions of a period of ring formation in the industrial kiln showed that the start location of calcination fluctuated by more than 2 m on either side of the mean of regular operation, warranting further investigation of the importance of these fluctuations on mid-kiln ring formation.
Journal articles
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Totally chlorine-free peracetic acid pulping for nanocellulose isolation from hemp and poplar, TAPPI Journal August 2023
ABSTRACT: Nanocellulose is a promising and sustainable feedstock for developing advanced and functional materials. However, the characteristics of nanocellulose, such as crystallinity, surface energy, and aspect ratio, can vary depending on biomass source and pretreatment methods, leading to variable performance of the nanocellulose-based materials. In this study, cellulose nanocrystals (CNCs) were isolated from hemp and poplar using totally chlorine free (TCF) peracetic acid and sodium chlorite delignification and bleaching pretreatments to probe the influences of biomass source and treatment methods on the isolation and characteristics of CNCs. Our results showed that hemp and poplar were almost completely delignified by peracetic acid treatment, whereas sodium chlorite treatment left 5%•6% lignin in the pulp. The yields of CNCs from raw hemp and poplar biomass ranged from 9.8% to 21.9% and 10.9% to 28.3%, respectively, depending on the treatment methods. The dimensions of CNCs from TCF-treated biomass generally maintained a larger width and aspect ratio than those from sodium chlorite-treated biomass. The poplar-derived CNCs exhibited slightly higher crystallinity of 53%•58% than hemp-derived CNCs of 49%•54%. The zeta potential of the CNCs, ranging from -20.1 mV to -31.1 mV, ensured a well-dispersed aqueous solution. The surface energy (dispersive energy of 40•80 mJ/m2 and specific energy of 2•10 mJ/m2), water interaction, and thermal stability of the CNCs were comparable, regardless of the biomass source and pretreatment methods. Our finding suggests that the TCF technique with peracetic acid treatment is a promising delignification and bleaching approach to obtain cellulose-rich pulps from herbaceous and hardwood biomass for nanocellulose isolation.
Journal articles
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SCC susceptibility of chromized type 409 stainless steel in alkaline chloride solutions at ambient temperature and pressure, TAPPI Journal August 2023
ABSTRACT: Biomass hydrothermal liquefaction (HTL) is operated in a harsh reaction medium that contains hot pressurized water, inorganic acidic or basic catalyst, and inorganic/organic corrosive components released during the conversion. Candidate alloys for this application require suitable resistance to both corrosion and stress corrosion cracking (SCC) to withstand the HTL process conditions (250°C•374°C and 4•22 MPa). Ferritic iron-chromium (Fe-Cr) steels are more prone to corrosion but less susceptible to SCC compared to austenitic iron-chromium-nickel (Fe-Cr-Ni) steels. Chromizing can significantly reduce corrosion of Type 409 stainless steel (Fe-11Cr) in a simulated aqueous HTL solution. The objective of this study is to determine the SCC susceptibility of chromized Type 409 stainless steel, relative to the bare (non-chromized) case. The slow strain rate testing (SSRT) technique was used for this purpose. For simplicity of experimentation, SSRT was conducted using simulated HTL water containing 800 ppm potassium chloride (KCl), 1 M potassium carbonate (K2CO3), and 10 wt% acetic acid at ambient temperature and pressure. Complementary potentiodynamic polarization measurements and surface analysis by X-ray photoelectron spectros-copy (XPS) were also made to help interpret the SSRT results. The SSRT results show no significant difference in SCC susceptibility, regardless of the starting surface. Thus, chromizing, while significantly reducing the corrosion of Type 409 stainless steel, does not adversely affect SCC susceptibility, at least under the conditions tested.