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Cross-flow separation characteristics and piloting of graphene oxide nanofiltration membrane sheets and tubes for kraft black liquor concentration, TAPPI Journal September 2023
ABSTRACT: Dewatering of weak black liquor (WBL) in the kraft cycle by evaporation is highly energy intensive. Membranes are an attractive alternative for energy-efficient dewatering, but existing commercial polymeric or ceramic membranes are either degraded in BL or have high capital costs. Our recent works have demonstrated the engineering of graphene oxide (GO) nanofiltration membranes, their stability and promising performance in BL conditions, and preliminary scale-up into sheets and tubes. Here, we describe in detail the separation characteristics of GO membrane sheets and tubes under real BL conditions and crossflow operation. Recycle-mode piloting of a GO tubular membrane showed average “production flux” of 16 L/m2/h (LMH) and high rejections of lignin (98.3%), total solids (66%), and total organic carbon (83%), with no signs of irreversible fouling identified. A corresponding GO sheet membrane produced an average flux of ~25 LMH and maintained high lignin rejection of ~97% during a slipstream pilot at a kraft mill site using WBL with ~16 wt% total solids (TS). Finally, we piloted a Dow/DuPont XUS1808 polyamide composite reverse osmosis (RO) membrane for last-mile processing of the GO nanofiltration membrane permeate. The RO membrane showed a steady state flux of 19 LMH at 65 bar and produced ~0.02 wt% TS water product, which is highly suitable for reuse in pulp washing operations in the kraft process. The results have strong positive implications for the industrial application of GO membranes in BL concentration and other related applications.
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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.
Journal articles
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Experiments and visualization of sprays from beer can and turbo liquor nozzles, TAPPI Journal February 2022
ABSTRACT: Industrial scale swirl-type black liquor nozzles were studied using water as the test fluid. Simple water spraying experiments were found to be very beneficial for studying and comparing nozzles for black liquor spraying. These kinds of experiments are important for finding better nozzle designs. Three nozzle designs were investigated to understand the functional differences between these nozzles. The pressure loss of nozzle 1 (“tangential swirl”) and nozzle 3 (“turbo”) were 97% and 38% higher compared to nozzle 2 (“tan-gential swirl”). Spray opening angles were 75°, 60°, and 35° for nozzles 1, 2, and 3, respectively. Video imaging showed that the nozzles produced sprays that were inclined a few degrees from the nozzle centerline. Spray patter-nation showed all the sprays to be asymmetric, while nozzle 2 was the most symmetric. Laser-Doppler measure-ments showed large differences in spray velocities between nozzles. The spray velocity for nozzle 1 increased from 9 m/s to 15 m/s when the flow rate was increased from 1.5 L/s to 2.5 L/s. The resulting velocity increase for nozzle 2 was from 7 m/s to 11 m/s, and for nozzle 3, it was from 8 m/s to 13 m/s. Tangential flow (swirl) directed the spray 6°•12° away from the vertical plane. Liquid sheet breakup mechanisms and lengths were estimated by analyzing high speed video images. The liquid sheet breakup mechanism for nozzle 1 was estimated to be wave formation, and the sheet length was estimated to be about 10 cm. Sheet breakup mechanisms for nozzle 2 were wave formation and sheet perforation, and the sheet length was about 20 cm. Nozzle 3 was not supposed to form a liquid sheet. Nozzle geometry was found to greatly affect spray characteristics.
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Dynamic out-of-plane compression of paperboard — Influence of impact velocity on the surface, TAPPI Journal February 2024
ABSTRACT: Processes that convert paperboard into finished products include, for example, printing, where the paperboard is subjected to rapid Z-directional (ZD) compression in the print nip. However, measuring and evaluating the relevant properties in the thickness direction of paperboard are not necessarily straightforward or easy. Measuring at relevant, millisecond deformation rates further complicates the problem. The aim of the present work is to elucidate some of the influences on the compressive stiffness. Both the initial material response and the overall compressibility of the paperboard is studied. In this project, the effect on the material response from the surface structure and the millisecond timescale recovery is explored.The method utilized is a machine called the Rapid ZD-tester. The device drops a probe in freefall on the substrate and records the probe position, thus acquiring the deformation of the substrate. The probe is also allowed to bounce several times on the surface for consecutive impacts before being lifted for the next drop. To investigate the time dependent stiffness behavior, the probe is dropped several times at the same XY position on the paperboard from different heights, thus achieving different impact velocities. The material response from drops and bounces combined allows study of the short-term recovery of the material. The material in the study is commercial paperboard. The paperboard samples are compared to material where the surface has been smoothed by grinding it. Our study shows that there is a non-permanent reduction in thickness and a stiffening per bounce of the probe, indicating a compaction that has not recovered in the millisecond timescale. Additionally, a higher impact velocity has an initial stiffening effect on the paperboard, and this is reduced by smoothing the surface.
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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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Kinetics of sulfur dioxide-alcohol-water (SAW) pulping of su
Kinetics of sulfur dioxide-alcohol-water (SAW) pulping of sugarcane straw (SCS), TAPPI JOURNAL June 2017
Journal articles
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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.
Journal articles
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Using bleaching stage models for benchmarking hardwood ECF bleach plants, TAPPI Journal October 2023
ABSTRACT: Steady-state models estimated the performance of the D0(EOP)D1 bleach sequence at two mixed hardwood bleach plants in the southern United States. At Mill 1, the full sequence’s chlorine dioxide charge that brightens the pulp to ~84% ISO was monitored for two weeks. Mill 2 considered the partial sequence that brightens the pulp to ~86% ISO for nearly four weeks. Elevated levels of chlorine dioxide were linked to increased washer carryover in brownstock and extraction areas. For Mills 1 and 2, an extra 0.24% and 0.33% chlorine dioxide was consumed in the D0 stage. This extra bleach demand was equivalent to an additional 4.8 and 5.5 kappa load to the brownstock, respectively. Some differences were observed for the D1 stage. Mill 1 had extraction carryover that averaged 1.1 units higher than was measured, contributing to use of an extra 0.22% of chlorine dioxide. Mill 2 had extraction carryover that averaged between 0 and 0.7 kappa units and consumed up to 0.13% more chlorine dioxide. Another data set from Mill 2 showed high brownstock and extraction carryover, leading to ~0.90% more total chlorine dioxide usage to brighten to 84% ISO. Overall, this investigation illustrated that the models could be employed as benchmarks.
Journal articles
Magazine articles
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.
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.