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Lignin-based resins for kraft paper applications, TAPPI Journal November 2019
ABSTRACT: We investigated miscanthus (MS) and willow (W) lignin-furfural based resins as potential reinforce-ment agents on softwood and hardwood kraft paper. These resins might be sustainable alternatives to the commercial phenolformaldehyde (PF) resins. Phenol is a petrochemical product and formaldehyde has been classified as a carcinogen by the U.S. Environmental Protection Agency. The lignin used in this study was derived from hot water extraction (160ºC, 2 h) of MS and W biomass, and may be considered sulfur-free. These biorefinery lignins were characterized for their chemical composition and inherent properties via wet chemistry and instrumental techniques. The resin blends (MS-resin and W-resin) were characterized for their molecular weight, thermal behavior, and mechanical properties. Mechanical properties were measured by the resin’s ability to reinforce softwood and hard-wood kraft papers. The effect of adding hexamethylenetetramine (HMTA), a curing agent, to the resin was also examined. Mixtures of PF and lignin-based resins were investigated to further explore ways to reduce use of non-renewables, phenol, and carcinogenic formaldehyde. The results show that lignin-based resins have the potential to replace PF resins in kraft paper applications. For softwood paper, the highest strength was achieved using W-resin, without HMTA (2.5 times greater than PF with HMTA). For hardwood paper, MS-resin with HMTA gave the highest strength (2.3 times higher than PF with HMTA). The lignin-based resins, without HMTA, also yielded mechanical properties comparable to PF with HMTA.
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Black liquor evaporator upgrades— life cycle cost analysis, TAPPI Journal March 2021
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. Evaporator steam economy is defined as the unit mass of steam required to evaporate a unit mass of water from black liquor (i.e., lb/lb or kg/kg.) The economy is determined by the number of effects in an evaporator train and the system configuration. Older systems use four to six effects, most of which are the long tube vertical rising film type. Newer systems may be designed with seven or even eight effects using falling film and forced circulation crystallization technology for high product solids. The median age of all North American evaporator systems is 44 years. Roughly 25% of the current North American operating systems are 54 years or older. Older systems require more periodic maintenance and have a higher risk of unplanned downtime. Also, older systems have chronic issues with persistent liquor and vapor leaks, shell wall thinning, corrosion, and plugged tubes. Often these issues worsen to the point of requiring rebuild or replacement. When considering the age, technology, and lower efficiency of older systems, a major rebuild or new system may be warranted. The intent of this paper is to review the current state of black liquor evaporator systems in North America and present a basic method for determining whether a major rebuild or new installation is warrant-ed using total life cycle cost analysis (LCCA).
Journal articles
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Can carbon capture be a new revenue opportunity for the pulp and paper sector?, TAPPI Journal August 2021
ABSTRACT: Transition towards carbon neutrality will require application of negative carbon emission technologies (NETs). This creates a new opportunity for the industry in the near future. The pulp and paper industry already utilizes vast amounts of biomass and produces large amounts of biogenic carbon dioxide. The industry is well poised for the use of bioenergy with carbon capture and storage (BECCS), which is considered as one of the key NETs. If the captured carbon dioxide can be used to manufacture green fuels to replace fossil ones, then this will generate a huge additional market where pulp and paper mills are on the front line. The objective of this study is to evaluate future trends and policies affecting the pulp and paper industry and to describe how a carbon neutral or carbon negative pulp and paper production process can be viable. Such policies include, as examples, price of carbon dioxide allowances or support for green fuel production and BECCS implementation. It is known that profitability differs depending on mill type, performance, energy efficiency, or carbon dioxide intensity. The results give fresh understanding on the potential for investing in negative emission technologies. Carbon capture or green fuel production can be economical with an emission trade system, depending on electricity price, green fuel price, negative emission credit, and a mill’s emission profile. However, feasibility does not seem to evidently correlate with the performance, technical age, or the measured efficiency of the mill.
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Investigation of the influencing factors in odor emission from wet-end white water, TAPPI Journal October 2020
ABSTRACT: Emission of malodorous gases, such as volatile organic compounds (VOCs), hydrogen sulfide (H2S), and ammonia (NH3) during pulping and papermaking has caused certain harm to the air environment and human health. This paper investigated the influencing factors of odor emission from wet-end white water during the production of bobbin paper in a papermaking mill using old corrugated containers (OCC) as raw material. The concentration of malodorous gases emitted from wet-end white water was determined with pump-suction gas detectors. The results indicated that low temperature could limit the release of malodorous gases from white water. Specifically, no total volatile organic compounds (TVOC), H2S, and NH3 was detected at a temperature of 15°C. The concentrations of malodorous gases were slightly increased when temperature increased to 25°C. When temperature was 55°C, the released concentrations of TVOC, H2S, and NH3 were 22.3 mg/m3, 5.91 mg/m3, and 2.78 mg/m3, respectively. Therefore, the content of malodorous gases significantly increased with the temperature increase. The stirring of white water accelerated the release of malodorous gases, and the release rate sped up as the stirring speed increased. However, the total amount of malodorous gases released were basically the same as the static state. Furthermore, the higher the concentration of white water, the greater the amount of malodorous gases released. The pH had little influence on the TVOC release, whereas it significantly affected the release of H2S and NH3. With the increase of pH value, the released amount of H2S and NH3 gradually decreased. When pH reached 9.0, the release amount of H2S and NH3 was almost zero, proving that an alkaline condition inhibits the release of H2S and NH3.
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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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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.
Journal articles
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Evaluation of soap recovery efficiency from black liquor — analytical tools, TAPPI Journal April 2023
ABSTRACT: Soap skimmings (“soap”) are typically recovered from black liquor in kraft mills that process a high percentage of softwood. In many mills, the recovery of soap is inefficient, negatively impacting performance of evaporators and recovery boilers and resulting in loss of potential revenue. A thorough evaluation of soap recovery performance in a kraft mill requires measurement of soap content in black liquor at various sampling locations, especially around the soap skimmer.The standard laboratory method for evaluating soap content in black liquor is a complex, multi-step process that relies on solvent extraction and titration; most mills send these samples to an outside laboratory for this analysis. In this study, 100 black liquor samples, with a wide range of soap concentrations, were tested by the standard solvent extraction method. After additional dilution, each sample was also tested for surface tension with a bubble pressure tensiometer. The results were found to correlate very closely with the solvent extraction tests results. This alternate method, using surface tension measurements of diluted black liquor samples, produces rapid results and can be easily implemented in most kraft mills, which would facilitate much more frequent in-house evaluations of soap recovery performance.
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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.
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.