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Value creation by converting pulp mill flue gas streams to green fuels, TAPPI Journal March 2023
ABSTRACT: Climate change mitigation induces strong growth in renewable electricity production, partly driven by shifts in environmental policies and regulation. Intermittent renewable electricity requires supporting systems in the form of sustainable hydrocarbon chemicals such as transportation fuels. Bulk chemical production fits well into a pulp mill environment, given their large volumes, stable operation, and ample supply of biomass-based carbon feed-stock in the form of flue gases. Until now, the utilization of the flue gases from conventional operation of a pulp mill has received little attention. Harnessing these flue gases into usable products could offer additional value to mill operators, while also diversifying their product portfolio. However, electricity-based fuels and products require extra energy in the conversion step and may not be commercially competitive with current fossil products under the current regulation. There might also be uncertainties about future commodity prices. Thus, the objective of this study is to estimate the economic competitiveness and the added value of selected side products that could be produced alongside conventional pulp and paper products. A typical modern pulp mill is modeled in different product configurations and operational environments, which allows testing of various development paths. This illustrates how the overall energy and mass balance of a pulp mill would react to changes in different final products and other parameters. The focus of the study is in synthetic methanol, which is produced from flue gases and excess resources from the mill, with minimal interference to the pulping process. The results aid in assessing the necessity and magnitude of a premium payment for subsidizing green alter-natives to replace current fossil fuels and chemicals. Additionally, the results function as an indicator of the development state of the pulp and paper industry in the turmoil of climate change regulation. The results indicate that power-to-X systems offer one more viable pathway alternative for broadening the product portfolio of the pulp and paper sector, as well as opening new flexibility measures and services to grid stabilization. Market conditions were found to have a significant impact on the perceived profitability.
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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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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
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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
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Control of malodorous gases emission from wet-end white water with hydrogen peroxide, TAPPI Journal October 2021
ABSTRACT: White water is highly recycled in the papermaking process so that its quality is easily deteriorated, thus producing lots of malodorous gases that are extremely harmful to human health and the environment. In this paper, the effect of hydrogen peroxide (H2O2) on the control of malodorous gases released from white water was investigated. The results showed that the released amount of total volatile organic compounds (TVOC) decreased gradually with the increase of H2O2 dosage. Specifically, the TVOC emission reached the minimum as the H2O2 dosage was 1.5 mmol/L, and meanwhile, the hydrogen sulfide (H2S) and ammonia (NH3) were almost completely removed. It was also found that pH had little effect on the release of TVOC as H2O2 was added, but it evidently affect-ed the release of H2S and NH3. When the pH value of the white water was changed to 4.0 or 9.0, the emission of TVOC decreased slightly, while both H2S and NH3 were completely removed in both cases. The ferrous ions (Fe2+) and the copper ions (Cu2+) were found to promote the generation of hydroxyl radicals (HO•) out of H2O2, enhancing its inhibition on the release of malodorous gases from white water. The Fe2+/H2O2 system and Cu2+/H2O2 system exhibited similar efficiency in inhibiting the TVOC releasing, whereas the Cu2+/H2O2 system showed better perfor-mance in removing H2S and NH3.
Journal articles
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Effects of carboxymethyl starch as a papermaking additive, TAPPI Journal February 2024
ABSTRACT: Carboxymethyl starch (CMS) is a bio-based, anionic polymer that has potential as part of a dry-strength additive program for papermaking. Due to its negative charge, its effects can be expected to depend on its interactions with various cationic agents. In this work, the effects of CMS were observed following its sequential addition after one of three selected cationic strength agents at different dosage levels. In selected tests, the furnish was pretreated at the 1% level by a dispersant, sodium polyacrylate, which might represent a high level of anionic contaminants in a paper mill system. Laboratory tests were conducted to show the effects on dewatering, fine-particle retention, and flocculation. These tests were supplemented with measurements of charge demand, zeta potential, and handsheet properties. Sequential addition of cationic glyoxylated acrylamide copolymers (gPAM) and CMS were found to strongly promote dewatering. Two gPAM products and a poly(vinylamine) product in sequential addition with CMS were very effective for promoting fine-particle retention. These same sequential treatments of the stock contributed to moderate fiber flocculation, though severe flocculation was caused by further treatment of the furnish with colloidal silica. Handsheet strength results were mixed. In the default recycled copy paper furnish, the average breaking length for the sheets made with cationic additives followed by CMS was not greatly different from the blank condition. Superior strength resulted when the default furnish was treated with a dispersant alone. When the dispersant-contaminated furnish was treated with the same combinations of cationic additives and CMS, the strength returned to the baseline achieved in the absence of the dispersant. The results were discussed in terms of the charged character of the different additives and their interactions not only with the fiber surfaces but also with each other.
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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
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: • The number of dirt specks larger than 250 µm in diameter increased as the ink coverage increased. • 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. • 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.