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Factors affecting phosphorus uptake/dissolution during slaking and causticizing, TAPPI Journal March 2024
ABSTRACT: Hydroxide is regenerated in the recovery cycle of kraft pulp mills by the addition of lime (CaO) to green liquor. Phosphate in green liquor can react with the lime during slaking/causticizing. Total titratable alkali (TTA), sulfidity, the concentration of phosphate in the green liquor, temperature, and the liming ratio were all variables explored in this work to determine their influence on phosphorus uptake and dissolution. Experiments were also run in which the lime was slaked before being added to the green liquor to separate reactions with phosphate during slaking and reactions that occur during causticizing. Both reburnt lime and technical grade CaO were used. The experiment results indicate that phosphorus primarily reacts with slaked lime (Ca(OH)2), and that the final concentration of phosphate in the white liquor at the end of slaking and causticizing is nearly independent of the initial concentration of phosphorus and only mildly dependent on the carbonate concentration in the green liquor. There do appear to be differences in the rate at which phosphate reacts with reburnt lime and technical grade CaO, though the reason for this was not determined.
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Editorial: TAPPI Journal Best Research Paper for 2023 focuses on black liquor concentration using graphene oxide membranes, TAPPI Journal February 2024
ABSTRACT: TAPPI and the TAPPI Journal (TJ) Editorial Board would like congratulate the authors of the 2023 TAPPI Journal Best Research Paper Award and Honghi Tran Prize: Sam Rae, Ella V. Richards, Max Kleiman-Lynch, Brent D. Keller, and Brandon I. Macdonald. Their paper, “Pilot scale black liquor concentration using pressure driven membrane separation,” appeared on p. 223 of the April 2023 issue. This kraft recovery cycle research was recognized by the TAPPI Journal Editorial Board for its innovation, creativity, scientific merit, and clear expression of ideas.
Journal articles
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Quantification of hardwood black liquor contamination in pine black liquor, TAPPI Journal February 2024
ABSTRACT: The presence of hardwood black liquor contamination in pine black liquor can negatively impact brownstock washer and evaporator operation, as well as reduce soap separation and yield. It is also believed to negatively impact commercial kraft lignin production. It was desired to develop a method of quantitatively determining the amount of low-level hardwood liquor contamination in pine black liquor. A method employing pyrolysis-gas chromatography mass spectrometry (py-GCMS) was developed to perform the desired measurement. Laboratory cooks with carefully controlled blends of pine and hardwood chips were prepared, and the resulting liquor was measured using this technique. Additionally, samples of pine and hardwood black liquors were blended in known quantities and analyzed. All these samples were submitted as blind samples. The resulting analysis suggests the py-GCMS method was able to accurately determine the level of hardwood contamination between 1% to 10% hardwood liquor using a low-level calibration curve prepared with coniferyl alcohol and sinapyl alcohol as standards.
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Eucalyptus black liquor properties in a lignin extraction process: density, dry solids, viscosity, inorganic, and organic content, TAPPI Journal March 2023
ABSTRACT: Extracting lignin from black liquor is becoming more common, although only a few research papers discuss the impact of the process on the liquor’s primary properties. This work aims to determine the changes in black liquor properties as it undergoes a lignin extraction process using carbon dioxide (CO2). A diluted eucalyptus black liquor sample (DBL) was acidified with CO2 to a final pH of 8.5. After filtration, the kraft lignin was removed, and the filtrated lignin lean black liquor (LLBL) was collected. Five acidified black liquors (ABL) samples were collected during acidification at pH 10.5; 10.0; 9.5; 9.0; and 8.5. The samples were analyzed regarding lignin content in solution, sodium carbonate (Na2CO3), sodium sulfate (Na2SO4), density, dry solids content, and viscosity. While Na2SO4 remained almost constant, Na2CO3 presented an enormous increase in its concentration when comparing DBL with LLBL. As pH decreased, the lignin content in the solution was also reduced due to lignin precipitation. The results showed similar behavior for dry solids, density, and viscosity of the supernatant, but an increase in density was observed around pH 9.00. In light of this, the density of LLBL turns out to be closer to the one in the initial DBL. The significant increase in carbonate content could explain this behavior during acidification with CO2 once the inorganic content significantly influences the property. The viscosity was determined from 10 s-1 to 2000 s-1. We observed a Newtonian behavior for all samples. The increase in carbonate content in the sample is crucial information to the recovery cycle, especially for calculating the mass and energy balance when targeting the use of the LLBL.
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On the diagnosis of a fouling condition in a kraft recovery boiler: combining process knowledge and data-based insights, TAPPI Journal March 2023
ABSTRACT: Fouling is still a major challenge for the operation of kraft recovery boilers. This problem is caused by accumulation of ash deposits on the surfaces of heat exchangers in the upper part of the boiler over time. The first consequence is the reduction of steam production due to loss of heat transfer and, finally, the shutdown of the boiler due to clogging. The present work investigated the operational condition of a modern kraft boiler under a critical fouling condition. This boiler had even faced a manual cleaning due to a clogging event. This analysis combined process knowledge, plant team experience, and a data-driven approach, given the complexity of the process. In this sense, historical data covering this critical period of operation were collected. After a cleaning procedure, they were used to obtain a predictive neural network model for the flue gas pressure drop in the boiler bank, which is an indirect measure of ash deposit accumulation. Once validated, it was used for sensitivity analysis, with the aim of quantifying the effects of the model inputs. Five variables out of eighteen accounted for nearly 60% of the total effect on pressure drop. Namely, primary air temperature (21.6% of the total effect) and flow rate (11.1%), black liquor flow rate (9.9%) and temperature (8.4%), and white liquor sulfidity (8.6%). The analysis of these results mainly suggested an excess of carryover, which composes the ash deposits. Recommended actions to mitigate the fouling condition involved adjustments to the primary air system before the more drastic solution of reducing the boiler load.
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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Techno-economic analysis of hydrothermal carbonization of pulp mill biosludge, TAPPI Journal March 2023
ABSTRACT: For many mills, the biosludge from wastewater treatment is difficult to recycle or dispose of. This makes it a challenging side stream and an important issue for chemical pulping. It often ends up being burned in the recovery or biomass boiler, although the moisture and non-process element (NPE) contents make it a problematic fuel. Biosludge has proven resistant to attempts to reduce its moisture. When incinerated in the biomass boiler, the heat from dry matter combustion is often insufficient to yield positive net heat. Mixing the sludge with black liquor in the evaporator plant for incineration in the recovery boiler is more energy efficient, but is still an additional load on the evaporator plant, as well as introducing NPEs to the liquor. In this study, treating the biosludge by hydrother-mal carbonization (HTC), a mild thermochemical conversion technology, is investigated. The HTC process has some notable advantages for biosludge treatment; taking place in water, it is well suited for sludge, and the hydrochar product is much easier to dewater than untreated sludge. In this study, two HTC plant designs are simulated using IPSEpro process simulation software, followed by economic analysis. Low temperature levels are used to minimize investment costs and steam consumption. The results show that if the sludge is incinerated in a biomass boiler, payback periods could be short at likely electricity prices. The HTC treatment before mixing the sludge with black liquor in the evaporator plant is profitable only if the freed evaporator capacity can be used to increase the firing liquor dry solids content.
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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Fiber-based characterization of pulp refining, TAPPI Journal September 2022
ABSTRACT: Fiber development in pulp refining can be characterized by three parameters: number of impacts on pulp, N; energy per impact, I, and bar force on fibers, F. These parameters enable comparisons of radically different refining conditions; determination of intensity for hardwoods and softwoods; assessment of effect of bar width on fiber shortening; and predictions of tensile strength increases.
Journal articles
Magazine articles
Using bleaching stage models for benchmarking softwood ECF bleach plants, TAPPI Journal July 2022
ABSTRACT: Steady-state bleaching delignification and brightening models were used to gauge how well elemental chlorine-free (ECF) bleach plants were using chlorine dioxide to bleach 25-kappa softwood brownstocks. Case 1 examined the D0(EOP)D1 portion of Mill 1’s five-stage sequence that brightens the pulp to 86% ISO. Case 2 studied the D0(EO)D1 portion of Mill 2’s four-stage sequence, which brightens the pulp to 82% ISO, and Case 3 re-examined the same bleach plant several years after it made improvements around the extraction stage. The models highlighted days in the previously mentioned cases where high bleach usage occurred, presumably because of high brownstock and/or extraction washer carryover, and days where bleach usage was normal. In Case 2, the model esti-mated that 10 kg of the 44 kg chlorine dioxide/metric ton pulp consumed in bleaching was likely reacting with washer carryover sources; approximately two-thirds of this extra consumption was assumed to be reacting with extraction filtrate. Changes that Mill 2 made (Case 3) reduced the unproductive chlorine dioxide usage from 10 to 5 kg/metric ton pulp. When the delignification and brightening models were simultaneously solved, the models predicted somewhat different optimized distributions of chlorine dioxide to D0 and D1 vs. actual values used in bleach plants. However, the forecasted chlorine dioxide totals agreed with the actual values when washer carryover sources were considered. This study showed the bleaching models could be used as hypothetical benchmarks for softwood ECF bleach plants.