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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.
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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.
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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.
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Commercially relevant water vapor barrier properties of high amylose starch acetates: Fact or fiction?, TAPPI Journal September 2021
ABSTRACT: Starches have recently regained attention as ecofriendly barrier materials due to the increased demand for sustainable packaging. They are easily processable by conventional plastics processing equipment and have been utilized for oil and grease barrier applications. While starches have excellent oxygen barrier properties and decent water barrier properties at low relative humidity (RH), they are moisture sensitive, as demonstrated by the deterioration of the barrier properties at higher RH values. Starch esters are chemically modified starches where the hydroxyl group of the starch has been substituted by other moieties such as acetates. This imparts hydrophobicity to starches and has been claimed as a good way of retaining water vapor barrier properties of starches, even at high RH conditions. We studied the water vapor barrier properties of one class of starch esters, i.e., high amylose starch acetates that were assumed to have good water vapor barrier properties. Our investigations found that with a high degree of substitution of hydroxyl groups, the modified starches did indeed show improvements in water vapor response as compared to pure high amylose starch films; however, the barrier properties were orders of magnitude lower than commercially used water vapor barriers like polyethylene. Even though these materials had improved water vapor barrier response, high amylose starch acetates are likely unsuitable as water vapor barriers by themselves, as implied by previous literature studies and patents.
Journal articles
Magazine articles
Comparative study of guar gum and its cationic derivatives as pre-flocculating polymers for PCC fillers in papermaking applications, TAPPI Journal April 2022
ABSTRACT: In this work, gums from guar seeds were evaluated as a potential precipitated calcium carbonate (PCC) filler pre-flocculant to induce functional filler in papermaking applications. In recent years, guar has been conidered one of the promising wet-end additives due to its abundance, rich source of hemicellulose content, and bio-degradability. However, application of guar gum in filler pretreatment methods for producing high ash paper has scarcely been reported. In this paper, the flocculating ability of three types of guar gum was established with charge analysis and turbidity (NTU) of the system at 1% and 5% for each gum: native gum (NG) having a degree of substitution (DS) of 0, and cationic gums having a DS value of 0.07 (CL) and 0.15 (CH). It was interesting to observe that even at a 5% dose of G, the charge density of PCC did not deviate much from the initial values. The system carried a weak negativeharge, resulting in an unstable colloidal suspension that led to PCC-PCC particle bridging. On the other hand, the operative mechanism of CL and CH during adsorption and PCC flocculation was predicted to be charge neutralization and electrostatic-patch formation, accompanied by particle bridging. Note that CL, with a maximum 47.5% eduction in residual turbidity of PCC at a 1% dose, was much more efficient in doing so than the other two gums; NG had a 40% maximum reduction in residual turbidity at a 5% dose and CH had a maximum 30% reduction at a 1% ose. Later on, floc formation and structure were correlated with optical and field emission scanning electron microscopy (FE-SEM) images. In the next set of trials, paper properties were determined by varying the different gum dosages from 0.2% to 5% at a constant dose of 20% filler. It is also noteworthy to mention that with 1% CL (low DS) dose, PCC retention increased by 39%, which also enhanced the tensile, tear, burst, and opacity properties by 11%, 19%, 5%, and 4.4%, respectively, without significantly affecting the bulk properties. Further, wide-angle X-ray diffraction (XRD) analysis nd Fourier transform infrared (FTIR) analysis revealed that pre-flocculating PCC with a 1% gum dose did not induce any change in crystalline transformation. Based on observation, it was found that cationic gums with low DS values re a better choice for maximizing the strength of paper while maintaining bulk and high opacity when pre-flocculaion is adopted to increase the filler retention in paper.
Journal articles
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Application of ATR-IR measurements to predict the deinking efficiency of UV-cured inks, TAPPI Journal January 2022
ABSTRACT: In recent years, ultraviolet (UV)-curable ink has been developed and widely used in various printing applications. However, using UV-printed products (UV prints) in recovered paper recycling causes end-product dirt specks and quality issues. A new method was developed that can distinguish UV prints from other prints by means of attenuated total reflectance infrared (ATR-IR) spectroscopy. Application of this method could allow more efficient use of UV prints as raw materials for paper recycling.First, a mill trial was performed using UV prints alone as raw materials in a deinked pulp (DIP) process. Second, test prints were made with four types of UV inks: a conventional UV ink and three different highly-sensitive UV inks. Each print sample had four levels of four-color ink coverage patterns (100%, 75%, 50%, and 25%). Next, deinkability of all prints was evaluated by laboratory experiments. Finally, each print was measured using the ATR-IR method, and the relationship between the IR spectra and deinkability was investigated. Mill trial results showed that UV prints caused more than 20 times as many dirt specks as those printed with conventional oil-based ink. There were variations in recycling performance among UV prints taken from bales used for the mill trial. Lab tests clearly revealed that not all UV-printed products lead to dirt specks. In order to clarify the factors that affected deinkability of UV prints, the print samples were investigated by lab experiments. Key findings from lab experiments include: œ The number of dirt specks larger than 250 µm in diameter increased as the ink coverage increased. œ Higher ink coverage area showed stronger intensity of ATR-IR spectral bands associated with inks. These results indicate that deinkability of UV prints could be predicted by analysis of ATR-IR spectra. œ Finally, the method was applied for assessment of recovered paper from commercial printing presses. It was confirmed that this method made it possible to distinguish easily deinkable UV prints from other UV prints. Based on these findings, we concluded that the ATR-IR method is applicable for inspection of incoming recovered paper.
Journal articles
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The use of minerals in fiber-based packaging and pulp molding, TAPPI Journal January 2024
ABSTRACT: Minerals are widely used in the pulp and paper industry for aiding the processing, economics, and final quality of fiber-based products. Among these, calcium carbonate, talc, and kaolin are widely used as fillers, and these can have varying brightness, particle size distributions, and aspect ratios. For the molded fiber area, these minerals can raise the solids content of the pulp mixture and improve throughput and lower energy requirements for drying. Talc is also widely used as a process control agent, picking up pitch and stickies and improving productivity by lowering machine cleaning time.The replacement of single use plastic with fiber-based replacements is a global trend; however, it does come with some significant challenges, such as grease and moisture proofing. Previously, per- and polyfluoroalkyl substances (PFAS) have been used to provide functions such as water and grease repellency, but regulatory demands have seen its demise in the packaging industry. Therefore, water holdout is now generally achieved by addition of alkyl ketene dimer (AKD) sizing. Wax additives are being developed and tested as PFAS replacements for oil and grease resistance. Rather than strongly repelling lipids from the fiber surface, these PFAS alternatives restrict flow pathways and react with food oils to alter their flow characteristics to prevent penetration through the substrate. During studies incorporating both PFAS substitutes and minerals, no detrimental interactions were observed. This paper addresses the different needs of the molded fiber market by including mineral fillers in molded fiber articles and will be presented as a series of different case studies. In all studies, we show that the trends observed when mineral filler is added to molded fiber are broadly similar to those seen in conventional paper and paperboard applications. Mineral addition in all studies gave improvements in productivity and optical appearance. With its organophilic surface, hydrophobic talc had the additional advantage of pitch and sticky control, and although a small decrease in strength was always observed when filler was added, the final articles still retained sufficient strength for their particular application. This small strength reduction should be balanced against the productivity gains.
Journal articles
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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
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Pilot scale black liquor concentration using pressure driven membrane separation, TAPPI Journal April 2023
ABSTRACT: Black liquor concentration using pressure driven membrane separation has long been proposed as a means of achieving energy savings and breaking production bottlenecks. To date, limitations in membrane performance and stability under black liquor process conditions have prevented those promises from being realized out-side of tightly controlled laboratory settings. In this work, we describe the first successful pilot scale field deployments of a membrane system for black liquor concentration. Using a purpose-built system and commercial sized, spiral wound graphene oxide membrane elements, we have logged nearly 6000 h of runtime across deployments to multiple mill sites. We demonstrate concentration of black liquor from 14% to >20% total solids, while generating permeate water comparable in quality to that of evaporator condensate and an 81% reduction in energy consumption relative to evaporation. At a commercial scale, these results translate to $2 M/year in net energy savings for a typical mill, as well as an opportunity to support production increases or mill expansions. These results represent a significant leap forward in the ability of membrane systems to deliver substantial value via black liquor concentration.