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Economic and competitive potential of lignin-based thermoplastics using a multicriteria decision-making method, TAPPI Journal September 2022
ABSTRACT: As a result of new lignin extraction plants hatching and increasing volumes of technical lignin becoming available, a variety of lignin derivatives, including phenolic resins and polyurethane (PU) foams, are reaching the marketplace or being used as intermediate products in many industrial applications. In the spectrum of possible lignin derivatives, thermoplastics appear particularly attractive due to a symbiosis of market, policy, and technology drivers. To assess the preferredness for lignin-based thermoplastics, this paper adapted a risk-oriented methodology formerly applied to assess lignin usage in various applications (phenol-formaldehyde [PF] resins, PU foams, and carbon fiber applications) to the case of lignin-based thermoplastics using hydroxypropylated lignin (HPL) and miscible blends of lignin and polyethylene oxide (PEO). The HPL is considered for garbage bags and agricultural films applications, while lignin-PEO blends are used as replacement for acrylonitrile butadiene styrene (ABS) in applications such as automotive parts. In the methodology, two phased-implementation strategies were defined for each thermoplastic derivative, considering perspectives for profit maximization (90 metric tons/day integrated units) and revenue growth (350 metric tons/day overall capacity), which were considered for implementation within a softwood kraft pulping mill. A set of six criteria representative of the main economic and market competitiveness issues were employed, and their respective importance weights were obtained in a multicriteria decision-making (MCDM) panel.Early-stage techno-economic estimates were done as a basis for the calculation of decision criteria. Compared to product derivatives previously assessed, capital investment for thermoplastic strategies appeared marginally higher due to the required lignin modification steps (on average 30% higher at similar capacity, and 6% for higher-scale revenue diversification strategies). Higher operating costs were also observed due to increased chemical expenses for all thermoplastic strategies, which are ultimately balanced by revenues associated with targeted thermoplastic products, leading to greater annual margins and cash flow generation over the project lifetime for thermoplastic strategies compared to other product applications (58% to 66% higher on average, at similar scale). Benefits of improved economics were reflected in economic criteria, internal rate of return (IRR), and cash flow on capital employed (CFCE), as well as in the price competitiveness criterion, CPC. Overall, the combination of relatively high lignin content in the plastic formulation and the less costly modification method contributed to lignin-PEO strategies, gaining the top two rankings. Based on their overall scores, both strategies defined for HPL would also integrate the group of “preferred” strategies, but are outranked by strategies that consider lignin positioning on PU foam applications.
Journal articles
Magazine articles
Experimental investigations into fold cracking of double coated barrier dispersion coatings, TAPPI Journal November 2024
ABSTRACT: The trend for replacing single-use plastics with fiber-based barrier coated board packaging has prompted a significant amount of research. There are many proposed ways of providing suitable packaging for applications like food service. Among these are dispersion coated barriers on board, as well as laminated boards that can be produced using conventional polyethylene (PE) or new biodegradable plastics. Minerals have also been shown to be suitable additives to these coatings for improving barrier performance through surface chemistry and by increasing the tortuosity of the pathway through the barrier layer. They also improve the cost effectiveness of the layer by lowering the material cost and raising the solids content, and by improving hold out of the functional layers, leading to a reduction in the amount of barrier coating needed to meet a given performance requirement. Minerals can also aid in the barrier handling in terms of rheology and reduced “stickiness,” as well as blocking of the films. When incorporated as fillers into extruded films, improved adhesion of the film to the board has been reported. One of the remaining challenges is the potential for cracking at the fold during converting and the loss of barrier performance that this can lead to. In this work, we systematically looked at the impact of mineral type and level in a dispersion coating. We assessed the differences in performance resulting from different coating application methods for the precoat layer by looking at the cracking tendency and loss of barrier functionality after folding for both the precoat alone and the final double coated sheets. Barrier results include moisture vapor transmission rate (MVTR), viscous vegetable oil, and the fluid blue stain in industrial methylated spirits (IMS) and Cobb water absorption, both before and after folding.
Journal articles
Paper strength factors in systems with nanofibrillated cellulose, cationic starch, colloidal silica, cationic acrylamide copolymer, and hydrodynamic shear, TAPPI Journal May 2025
ABSTRACT: Laboratory paper sheets were formed by first pretreating nanofibrillated cellulose (NFC) with cationic starch at the 5% level by mass. The treated NFC was then added to stock prepared from 100% recycled copy paper. The combined furnish was next optionally treated with a cationic retention aid (cPAM, 0.1%) and then colloidal silica (0.1% or 0.2%). Vacuum dewatering, fine-particle retention, and several paper properties were studied as a function of the colloidal silica level (zero, 1%, and 2%) and at different levels of shear stress applied just before forming the sheets. Dewatering and strength results were generally more favorable when using a medium charge cationic starch (~ 0.03 degree of substitution, DS) to pretreat the NFC rather than a high charge density cationic starch (~ 0.2 DS). In each case, the dewatering was further enhanced by subsequent treatments by cPAM (0.1% on whole furnish solids) and then even more with the final addition of colloidal silica (0.1% and 0.2% levels compared). However, the colloidal silica additions progressively hurt the tensile strength of the paper, especially in the case of the high charge cationic starch and at the higher level of colloidal silica. Though the dewatering performance was favorable, in such cases, the paper strength was not improved compared to paper made without any NFC. The fact that the systems involving cPAM treatment, and especially those involving both cPAM and colloidal silica, tended to reduce the resulting paper’s tensile strength supports a mechanism in which the additives result in the clustering of the NFC, possibly in multiparticle bunches. Evidence suggests that such bunches of clustered NFC particles, which are difficult to redisperse even at levels of hydrodynamic shear present in high-speed paper machine systems, are resistant to full integration into the sheet structure as the paper is being formed.
Journal articles
Magazine articles
Boiler retrofit improves efficiency and increases biomass firing rates, TAPPI Journal March 2021
ABSTRACT: Domtar’s fluff pulp mill in Plymouth, NC, USA, operates two biomass/hog fuel fired boilers (HFBs). For energy consolidation and reliability improvement, Domtar wanted to decommission the No. 1 HFB and refurbish/retrofit the No. 2 HFB. The No. 2 HFB was designed to burn pulverized coal and/or biomass on a traveling grate. The steaming capacity was 500,000 lb/h from coal and 400,000 lb/h from biomass. However, it had never sustained this design biomass steaming rate. As the sole power boiler, the No. 2 HFB would need to sustain 400,000 lb/h of biomass steam during peak loads. An extensive evaluation by a combustion and boiler technologies supplier was undertaken. The evaluation involved field testing, analysis, and computational fluid dynamics (CFD) modeling, and it identified several bottle-necks and deficiencies to achieving the No. 2 HFB’s biomass steam goal. These bottlenecks included an inadequate combustion system; insufficient heat capture; excessive combustion air temperature; inadequate sweetwater con-denser (SWC) capacity; and limited induced draft fan capacity.To address the identified deficiencies, various upgrades were engineered and implemented. These upgrades included modern pneumatic fuel distributors; a modern sidewall, interlaced overfire air (OFA) system; a new, larger economizer; modified feedwater piping to increase SWC capacity; replacement of the scrubber with a dry electrostatic precipitator; and upgraded boiler controls.With the deployment of these upgrades, the No. 2 HFB achieved the targeted biomass steaming rate of 400,000 lb/h, along with lowered stack gas and combustion air temperatures. All mandated emissions limit tests at 500,000 lb/h of steam with 400,000 lb/h of biomass steam were passed, and Domtar reports a 10% reduction in fuel firing rates, which represents significant fuel savings. In addition, the mill was able to decommission the No. 1 HFB, which has substantially lowered operating and maintenance costs.
Journal articles
Physico-mechanical and ethylene scavenging properties of active packaging from Bambusa fibers modified with TiO2 /Cu2O composite, TAPPI Journal February 2026
ABSTRACT: The physico-mechanical and ethylene scavenging properties of active packaging consisting of paper prepared from bamboo (Bambusa vulgaris) fibers loaded with varying concentrations of nano titanium dioxide/cuprous oxide (TiO2/Cu2O) composite was investigated for its ability to delay ripening of Philippine climacteric fruits. Tests of paper containing 1% to 5% TiO2/Cu2O showed no or limited negative impact on its physical, optical, and mechanical properties. Images from a field emission scanning electron microscope equipped with energy-dispersive X-ray spectroscopy (FESEM-EDS) showed dispersion and agglomeration of TiO2/Cu2O nanoparticles on the paper surface. The percent weight of titanium and copper increased with increasing metal oxide composite concentration used in this study. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy indicated small shifts in band intensity at 3330 cm-1 and 1100 cm-1 in the hydroxyl (O-H) and C-O regions, respectively, suggesting possible chemical or physical interactions between the metal oxide and paper. Contact angle measurement suggest- ed that TiO2/Cu2O nanoparticles may have imparted paper hydrophobicity at 3% & 5% concentration, possibly through increased microscale roughness. The ethylene scavenging experiment indicated that there was a significant delay in the ripening process of mango and tomato when packed in paper doped with 3% and 5% TiO2/Cu2O. The fruits were greener with a firmer texture compared with untreated control after three days of storage under natural light and ambient condition. The preliminary results suggested that 3% &5% TiO2/Cu2O active packaging modification can remove ethylene from the fruit's storage environment, extending shelf life and maintain quality for three days. This simple technique could have potential economic benefits for the fruit industry by directly reducing post-harvest waste, and the delayed ripening could provide flexibility in supply chain management.
Journal articles
Non-process elements in the lime cycle: New findings regarding NPE distribution and lime mud filterability, TAPPI Journal July 2026
ABSTRACT: Proper functioning of the recausticizing cycle is crucial for securing a stable white liquor supply for a pulp mill. Common runnability problems in the modern lime cycle, such as low filterability and poor dewatering of lime mud, high dead load, or ring formation in the lime kiln, are often caused by accumulation of non-process elements (NPEs). This project attempted to verify the traditional rules of thumb regarding the chemical behavior of NPEs: magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu), barium (Ba), cadmium (Cd), and lead (Pb) in the causticizing reaction, and to investigate the reasons behind poor lime mud filterability. First, a standardized method for measuring filterability of lime mud was developed. Next, a series of recausticizing experiments, followed by immediate filtration trials, was conducted using mill green liquors, laboratory-made synthetic green liquor, reburned lime/makeup mix, and extra NPE additions. It was found that sodium (Na), potassium (K), and sulfur (S) followed the liquid phase, as expected, while Mg, P, and Ba, but also Pb, Cu, and Cd, showed low solubility and accumulated in the lime mud. The Si and Al accumulated in the lime mud even though the soluble content in liquor was high, while the behavior of Mn, Fe, and Zn was more complex. Based on these results, tentative solubility limits for NPEs were suggested as a first estimate for the maximum possible concentrations of NPEs in mill white liquor. The causticization-filtration experiments revealed that overliming and high content of Mg in green liquor clearly led to lower filterability, but our addition of Si did not have such an effect. As differences in particle size and size distribution have a certain impact on the filtration resistance, the lime mud sedimentation behavior, combined with other characterization methods, might be used as an indication for the filterability. Finally, a list of recommendations for pulp mills was formulated that starts with establishing a comprehensive standard for a lime mud with good filterability. This standard can be used as a benchmark for comparison any time a lime cycle runnability problem is identified.
Journal articles
Black liquor spray properties in-furnace conditions for swirl cone nozzles, TAPPI Journal July 2026
ABSTRACT: Recovery boiler furnace operation is controlled for high chemical recovery, high steam production, and low emissions. Good control allows long runs with minimum cleaning without expensive shutdowns. An essential variable affecting boiler operation is black liquor spraying into the furnace. Poorly controlled black liquor spraying causes difficulties, e.g., in chemical recovery, fouling of heat transfer surfaces, and decreased energy production. A challenging measurement strategy with three different swirl cone nozzles . types A, C, and T . was carried out at a mill in the United States. Black liquor spray properties were measured under in-furnace conditions for flow rates of 2.0 L/s to 3.0 L/s. Three spraying temperatures of 119™‹C, 122™‹C, and 126™‹C, which were 2™‹C, 5™‹C, and 9™‹C above the boiling point (ƒ¢Te), were tested. These flow rates and temperatures are typical for industrial nozzle sizes with exit orifice sizes of 17 mm and 22 mm. An imaging method to measure droplet size in a highly challenging furnace environment was developed. Droplet volume median diameter (Dv50) for nozzles A, C, and T varied between 7 mm to 4 mm, 7 mm to 5 mm, and 8 mm to 6 mm, depending on the flow rate and temperature. The high number of droplets detected by the analysis program enabled data fitting into statistical correlations. The size and width parameters for the Rosin™]Rammer droplet size distribution function could be defined. The droplet size distribution was found to be surprisingly wide, probably because of swollen droplets. Spray velocity was measured in two locations, 5 cm from the nozzle and 1.8 m from the nozzle. Near the nozzle, the average velocity increased from 7.3 m/s to 13 m/s when the flow rate was increased from 2 L/s to 3 L/s. Increase of black liquor temperature increased spray velocity in most of the cases. At the distance of 1.8 m from the nozzle, average spray velocities varied between 4.0 m/s to 11 m/s, depending on nozzle geometry, flow rate, and temperature. The opening angles of the spray for nozzles A and C varied between 57™‹ to 78™‹. The opening angle of nozzle T with flow guide varied between 48™‹ to 56™‹. The highest penetration of the spray was estimated for nozzle T because of the narrow spray and large droplets.
Journal articles
Exploratory study on how sub-ply fiber orientation affects t
ABSTRACT: The transition to 100% biobased packaging presents considerable challenges, particularly in the development of a petroleum-free barrier. Generally, biobased barriers exhibit lower flexibility compared to traditional barriers, thereby increasing the risk of cracking during the converting process. The present study examines the possibility of optimizing the substrate to reduce cracking in brittle barriers. Five three-ply composites were fabricated using commercial paperboard to enable a composite with different fiber orientation in the individual plies. The different orientations achieved varying mechanical properties, including strain-atbreak and folding resistance, with a ranking that is comparable to a standard multi-ply paperboard. The composites were subjected to creasing at five distinct depths to assess the area percent of barrier cracks across the crease bead. Micro-cracks appeared on the surface before larger coating cracks were registered. As expected, the area percent of barrier cracks increased significantly with greater creasing depths. The orientation of the bulky middle ply showed little difference in the cracking propensity. However, by replacing the stiffer bottom ply with a ply of lower stiffness, the cracking propensity was significantly reduced without a substantial loss in mechanical properties. Hence, these findings indicate that it is possible to reduce the cracks in the barrier by modifying the fiber orientation in the different plies.
Journal articles
Improving barrier performance of coated paper and paperboard
ABSTRACT: Market demand for barrier coated packaging paper and paperboard has been on a steady rise and is forecasted to further increase. As a result, there is a continued interest in improving barrier coating functionalities, which is currently an active area of investigation. In this work, a multi-layer approach was adopted that involved applying a biowax emulsion, latex, or a combination of biowax and latex top coating layer onto the kaolin/latex (20/80, 50/50, 65/35, or 70/30) precoated solid bleached sulfate (SBS) paperboard. Our main objective was to demonstrate the effect of these top coating layers on various barrier properties, especially water vapor transmission rate (WVTR) at high relative humidity (RH) and high temperature (90% RH; 38°C), known as tropical/jungle test conditions. While the top coat with latex and/or biowax showed dramatic improvement in both water resistance (Cobb) and WVTR, the biowax coating increased contact angle significantly compared to the latex top coat. Contact angle increased from about 65° for the latex top coat to as high as 96° for the biowax top coat. Generally, it is much more difficult to improve WVTR at the jungle conditions below 100 g/m2/day, even with the high aspect ratio platy pigment. However, using the coating strategies adopted in this study, we were able to achieve WVTR values notably below 50 g/m2/day at the tropical test conditions, as well as significant improvements in regard to fold crack barrier integrity at high kaolin clay usage.
Journal articles
Prediction of residual calcium carbonate (CaCO3) in the lime
ABSTRACT: In a kraft pulp mill, the rotary lime kiln is responsible for converting calcium carbonate (CaCO3) into calcium oxide (CaO) to be reused in the causticizing plant. An important parameter of the calcination efficiency and the product quality is the amount of CaCO3 not converted to CaO, commonly defined as residual carbonate. This parameter is usually determined through laboratory analysis, which introduces delays in process control and limits the ability to make timely operational adjustments. This work presents a predictive model that functions as a soft sensor for the residual carbonate in a lime kiln of a Brazilian kraft pulp mill. This model was able to estimate residual CaCO3 every 30 min using routinely measured online process variables, which is a considerable reduction from the 6-h average laboratory measurement. The correlation coefficient (r) between the model predictions and the mill values was 0.83, with a mean absolute error (MAE) of 0.33%. Considering the effect of the residence time throughout the lime kiln proved to be decisive in obtaining a satisfactory prediction result. After model validation, a variable importance analysis showed that the carbon monoxide (CO) concentration in the stack flue gas (in ppm), secondary air temperature (in oC), and fan speed (in %) were the most influential variables in predicting the residual carbonate content. Combined with commonly used operation expertise, this subset of variables can serve as additional information to achieve smoother lime kiln operation.