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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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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.
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Numerical analysis of the impact of rotor and screen hole plate design on the performance of a vertical pulper, TAPPI Journal April 2025
ABSTRACT: The dissolving of mechanical pulp is one of the most important process steps in stock preparation, since pulping occurs at the very beginning of the papermaking process. Efficient mixing of the pulp in a short amount of time is essential to achieve high furnish volume flow rates. The design of the rotor, as well as the pulper vat and inserts, significantly affects the overall performance of the pulper, such as mixing efficiency and power demand. Using advanced numerical methods such as computational fluid dynamics (CFD) can accelerate the development process. The CFD simulations allow for detailed analysis of flow phenomena, making it possible to study a real-size machine numerically. This approach is particularly advantageous because it can reduce the need for timeconsuming and costly experiments associated with scaling up test rigs. In this study, we compared two different rotor designs utilized in a vertical pulper and evaluated the numerical results with experimental data. Rotor A is designed for low turbulence and low power demand, while rotor B is designed for high turbulence with high power demand. The CFD results showed good agreement with the experimental measurements. We investigated how the rotor design influences the free fluid surface and the mixing efficiency. Our study also highlights the differences in results depending on whether water or furnish is simulated, which exhibit Newtonian or, respectively, non-Newtonian fluid behavior. Additionally, a detailed numerical investigation of various screen hole plate designs revealed that the newly developed hole design significantly reduces pressure loss compared to a standard drilled hole. This outcome was consistent for both types of fluids investigated: water and furnish.
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Preparation of regenerated cellulose from rice straw lignocellulosic waste and its use for reinforced paper products, TAPPI Journal July 2021
ABSTRACT: Rice straw waste is a lignocellulosic waste produced by farmers in large quantities. In this study, regenerated cellulose (RC) from rice straw was prepared by dissolving rice straw holocellulose (HC) in NaOH/Urea/Thio-urea/Water solution by the freeze-thawing process. The crystallinity index of RC was calculated at 31%, which is out of the crystallinity range of 39%•69% that has been previously suggested.The study indicated that the RC is amorphous with a low degree of polymerization (638) and higher hydroxyl group content as compared to HC. The fiber length of RC was found to be 26.7% shorter; however, the width of RC was 21.2% higher as compared to HC. Reduced kinked fiber content was observed in the fraction of RC (18.3%) as compared with HC (39.1%), and a higher curl index of fiber was observed more so in HC (10.5%) than RC (5.6%). Because of the regeneration process, the fiber length was reduced and a fines element content of about 96% was observed in RC compared to the initial fines content of HC (56.9%). Irrespective of the high fines element content of RC, the composite paper of rice straw bleached pulp and RC fibers was developed with an increase in the tensile index from 41.4 N.m/g to 71.2 N.m/g and an increase in the burst index from 4.7 kPa.m2/g to 5.3 kPa.m2/g with the addition of 5% and 15% RC, respectively. However, enhanced tear index of paper was observed up to 5% and then it declined upon further addition of RC. The study revealed that regenerated cellulose can be used as a strength additive to overcome the shortcomings of low mechanical properties in paper products.
Journal articles
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Rethinking the paper cup — beginning with extrusion process optimization for compostability and recyclability, TAPPI Journal June 2021
ABSTRACT: More than 50 billion disposable paper cups used for cold and hot beverages are sold within the United States each year. Most of the cups are coated with a thin layer of plastic — low density polyethylene (LDPE) — to prevent leaking and staining. While the paper in these cups is both recyclable and compostable, the LDPE coat-ing is neither. In recycling a paper cup, the paper is separated from the plastic lining. The paper is sent to be recycled and the plastic lining is typically sent to landfill. In an industrial composting environment, the paper and lining can be composted together if the lining is made from compostable materials. Coating paper cups with a compostable performance material uniquely allows for used cups to be processed by either recycling or composting, thus creating multiple pathways for these products to flow through a circular economy.A segment of the paper converting industry frequently uses an extrusion grade of polylactic acid (PLA) for zero-waste venues and for municipalities with ordinances for local composting and food service items. The results among these early adopters reveal process inefficiencies that elevate manufacturing costs while increasing scrap and generally lowering output when using PLA for extrusion coating. NatureWorks and Sung An Machinery (SAM) North America researched the extrusion coating process utilizing the incumbent polymer (LDPE) and PLA. The trademarked Ingeo 1102 is a new, compostable, and bio-based PLA grade that is specifically designed for the extrusion coating process. The research team identified the optimum process parameters for new, dedicated PLA extrusion coating lines. The team also identified changes to existing LDPE extrusion lines that processors can make today to improve output.The key finding is that LDPE and PLA are significantly different polymers and that processing them on the same equipment without modification of systems and/or setpoints can be the root cause of inefficiencies. These polymers each have unique processing requirements with inverse responses. Fine tuning existing systems may improve over-all output for the biopolymer without capital investment, and this study showed an increase in line speed of 130% by making these adjustments. However, the researchers found that highest productivity can be achieved by specifying new systems for PLA. A line speed increase to more than 180% and a reduction in coat weight to 8.6 µm (10.6 g/m2 or 6.5 lb/3000 ft2) was achieved in this study. These results show that Ingeo 1102 could be used as a paper coating beyond cups.
Journal articles
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Probing the molecular weights of sweetgum and pine kraft lignin fractions, TAPPI Journal June 2021
ABSTRACT: The present investigation undertook a systematic investigation of the molecular weight (MW) of kraft lignins throughout the pulping process to establish a correlation between MW and lignin recovery at different extents of the kraft pulping process. The evaluation of MW is crucial for lignin characterization and utilization, since it is known to influence the kinetics of lignin reactivity and its resultant physico-chemical properties. Sweetgum and pine lignins precipitated from black liquor at different pHs (9.5 and 2.5) and different extents of kraft pulping (30•150 min) were the subject of this effort. Gel permeation chromatography (GPC) was used to determine the number average molecular weight (Mn), mass average molecular weight (Mw), and polydispersity of the lignin samples. It was shown that the MW of lignins from both feedstocks follow gel degradation theory; that is, at the onset of the kraft pulping process low molecular weight-lignins were obtained, and as pulping progressed, the molecular weight peaked and subsequently decreased. An important finding was that acetobromination was shown to be a more effective derivatization technique for carbohydrates containing lignins than acetylation, the technique typically used for derivatization of lignin.
Journal articles
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Soybean peroxidase treatment of ultra-high kappa softwood pulp to enhance yield and physical properties, TAPPI Journal September 2020
ABSTRACT: The working hypothesis serving as basis for this study is that pulping to a higher kappa number will produce a higher yield pulp, and then treating that pulp with a surface reactive lignin peroxidase to ablate surface lignin will increase specific bonding area. In the present case, the working hypothesis was modified so that soybean peroxidase (SBP) works like lignin peroxidase to modify surface lignin on high-kappa, high-yield softwood pulps to facilitate enhanced fiber-to-fiber bonding such that the resulting paper strength is similar to the lower kappa soft-wood pulp generally used to make linerboard. Soybean peroxidase is actually a plant peroxidase that exhibits lignin peroxidase-like activity. It is not a lignin peroxidase derived from white rot fungus. The current work did show a significant improvement in pulp yield (62.2% vs. 55.2% yield for a 103-kappa control linerboard grade sheet), while treatment with SBP showed that tensile, burst, and STFI properties of the pulp were improved, although more convincing data needs to be obtained.
Journal articles
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Lignin carbohydrate complex studies during kraft pulping for producing paper grade pulp from birch, TAPPI Journal September 2020
ABSTRACT: Paper grade pulp production across the globe is dominated by the kraft process using different lignocellulosic raw materials. Delignification is achieved around 90% using different chemical treatments. A bottleneck for complete delignification is the presence of residual covalent bonds that prevail between lignin and carbohydrate even after severe chemical pulping and oxygen delignification steps. Different covalent bonds are present in native wood that sustain drastic pulping conditions. In this study, 100% birch wood was used for producing paper grade pulp, and the lignin carbohydrate bonds were analyzed at different stages of the kraft cook. The lignin carbohydrate bonds that were responsible for residual lignin retention in unbleached pulp were compared and analyzed with the original lignin-carbohydrate complex (LCC) bonds in native birch wood. It was shown that lignin remaining after pulping and oxygen delignification was mainly bound to xylan, whereas the lignin bound to glucomannan was for the most part degraded.
Journal articles
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Quantification of vegetable oil in recycled paper, TAPPI JOURNAL September 2020
ABSTRACT: Vegetable soybean oil is commonly used in cooking foods that are packaged in takeaway paper-board containers. Vegetable oil is hydrophobic, and in sufficiently high concentration, could interfere with interfiber bonding and result in paper strength loss. In order to quantify the effect of oil on the resulting paperboard strength, it is necessary to quantify the oil content in paper. A lab method was evaluated to determine the soybean oil content in paper. Handsheets were made with pulps previously treated with different proportions of vegetable oil. Pyrolysis gas chromatography-mass spectrometry (pyGCMS) was used to quantify the amount of oil left in the handsheets. The results revealed a strong correlation between the amount of oil applied to the initial pulp and the amount of oil left in the handsheets.In addition, the effect of vegetable oils on paper strength may be affected by the cooking process. Vegetable oil is known to degrade over time in the presence of oxygen, light, and temperature. The vegetable oil was put in an oven to imitate the oil lifecycle during a typical pizza cooking process. The cooked oil was then left at room temperature and not protected from air (oxygen) or from normal daylight. The heated, then cooled, oil was stored over a period of 13 weeks. During this time, samples of the aged oil were tested as part of a time-based degradation study of the cooked and cooled oil.