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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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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
Non-process elements in the lime cycle: New findings regarding NPE distribution and lime mud filterability, TAPPI Journal July 2026
ABSTRACT: Proper functioning of the recausticizing cycle is crucial for securing a stable white liquor supply for a pulp mill. Common runnability problems in the modern lime cycle, such as low filterability and poor dewatering of lime mud, high dead load, or ring formation in the lime kiln, are often caused by accumulation of non-process elements (NPEs). This project attempted to verify the traditional rules of thumb regarding the chemical behavior of NPEs: magnesium (Mg), aluminum (Al), silicon (Si), phosphorus (P), zinc (Zn), manganese (Mn), iron (Fe), copper (Cu), barium (Ba), cadmium (Cd), and lead (Pb) in the causticizing reaction, and to investigate the reasons behind poor lime mud filterability. First, a standardized method for measuring filterability of lime mud was developed. Next, a series of recausticizing experiments, followed by immediate filtration trials, was conducted using mill green liquors, laboratory-made synthetic green liquor, reburned lime/makeup mix, and extra NPE additions. It was found that sodium (Na), potassium (K), and sulfur (S) followed the liquid phase, as expected, while Mg, P, and Ba, but also Pb, Cu, and Cd, showed low solubility and accumulated in the lime mud. The Si and Al accumulated in the lime mud even though the soluble content in liquor was high, while the behavior of Mn, Fe, and Zn was more complex. Based on these results, tentative solubility limits for NPEs were suggested as a first estimate for the maximum possible concentrations of NPEs in mill white liquor. The causticization-filtration experiments revealed that overliming and high content of Mg in green liquor clearly led to lower filterability, but our addition of Si did not have such an effect. As differences in particle size and size distribution have a certain impact on the filtration resistance, the lime mud sedimentation behavior, combined with other characterization methods, might be used as an indication for the filterability. Finally, a list of recommendations for pulp mills was formulated that starts with establishing a comprehensive standard for a lime mud with good filterability. This standard can be used as a benchmark for comparison any time a lime cycle runnability problem is identified.
Journal articles
Black liquor spray properties in-furnace conditions for swirl cone nozzles, TAPPI Journal July 2026
ABSTRACT: Recovery boiler furnace operation is controlled for high chemical recovery, high steam production, and low emissions. Good control allows long runs with minimum cleaning without expensive shutdowns. An essential variable affecting boiler operation is black liquor spraying into the furnace. Poorly controlled black liquor spraying causes difficulties, e.g., in chemical recovery, fouling of heat transfer surfaces, and decreased energy production. A challenging measurement strategy with three different swirl cone nozzles . types A, C, and T . was carried out at a mill in the United States. Black liquor spray properties were measured under in-furnace conditions for flow rates of 2.0 L/s to 3.0 L/s. Three spraying temperatures of 119™‹C, 122™‹C, and 126™‹C, which were 2™‹C, 5™‹C, and 9™‹C above the boiling point (ƒ¢Te), were tested. These flow rates and temperatures are typical for industrial nozzle sizes with exit orifice sizes of 17 mm and 22 mm. An imaging method to measure droplet size in a highly challenging furnace environment was developed. Droplet volume median diameter (Dv50) for nozzles A, C, and T varied between 7 mm to 4 mm, 7 mm to 5 mm, and 8 mm to 6 mm, depending on the flow rate and temperature. The high number of droplets detected by the analysis program enabled data fitting into statistical correlations. The size and width parameters for the Rosin™]Rammer droplet size distribution function could be defined. The droplet size distribution was found to be surprisingly wide, probably because of swollen droplets. Spray velocity was measured in two locations, 5 cm from the nozzle and 1.8 m from the nozzle. Near the nozzle, the average velocity increased from 7.3 m/s to 13 m/s when the flow rate was increased from 2 L/s to 3 L/s. Increase of black liquor temperature increased spray velocity in most of the cases. At the distance of 1.8 m from the nozzle, average spray velocities varied between 4.0 m/s to 11 m/s, depending on nozzle geometry, flow rate, and temperature. The opening angles of the spray for nozzles A and C varied between 57™‹ to 78™‹. The opening angle of nozzle T with flow guide varied between 48™‹ to 56™‹. The highest penetration of the spray was estimated for nozzle T because of the narrow spray and large droplets.
Journal articles
Magazine articles
Understanding the risks and rewards of using 50% vs. 10% strength peroxide in pulp bleach plants,TAPPI Journal December 2024
Authors: Alan W. Rudie and Peter W. Hart | TAPPI J. 17(11): 601(2018) - ABSTRACT: The use of 50% concentration and 10% concentration hydrogen peroxide were evaluated for chemical and mechanical pulp bleach plants at storage and at point of use. Several dangerous occurrences have been documented when the supply of 50% peroxide going into the pulping process was not stopped during a process failure. Startup conditions and leaking block valves during maintenance outages have also contributed to explosions. Although hazardous events have occurred, 50% peroxide can be stored safely with proper precautions and engineering controls. For point of use in a chemical bleach plant, it is recommended to dilute the peroxide to 10% prior to application, because risk does not outweigh the benefit. For point of use in a mechanical bleach plant, it is recommended to use 50% peroxide going into a bleach liquor mixing system that includes the other chemicals used to maintain the brightening reaction rate. When 50% peroxide is used, it is critical that proper engineering controls are used to mitigate any risks.
Journal articles
Magazine articles
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.
Journal articles
Magazine articles
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
Magazine articles
Production of antimicrobial paper using nanosilver, nanocellulose, and chitosan from a coronavirus perspective, TAPPI Journal July 2021
ABSTRACT: The pulp and paper industry has an opportunity to play a vital role in breaking the spread of the COVID-19 pandemic through production that supports widespread use of antimicrobial paper. This paper provides a brief review of paper and paper-related industries, such as those producing relevant additives, and R&D organizations that are actively engaged in developing antimicrobial papers. The focus here is on the potential of three nano-additives for use in production of antimicrobial papers that combat coronavirus: nanosilver, nanocellulose, and chitosan. Various recent developments in relevant areas and concepts underlining the fight against coronavirus are also covered, as are related terms and concepts.
Journal articles
Magazine articles
Addressing production bottlenecks and brownstock washer optimization via a membrane concentration system, TAPPI Journal July 2021
ABSTRACT: Advancements in membrane systems indicate that they will soon be robust enough to concentrate weak black liquor. To date, the economic impact of membrane systems on brownstock washing in kraft mills has not been studied and is necessary to understand the viability of these emerging systems and their best utilization.This study investigated the savings that a membrane system can generate related to brownstock washing. We found that evaporation costs are the primary barrier for mills seeking to increase wash water usage. Without these additional evaporation costs, we showed that our hypothetical 1000 tons/day bleached and brown pulp mills can achieve annual savings of over $1.0 MM when operating at higher dilution factors and fixed pulp production rate. We then investigated the impact of increasing pulp production on mills limited by their equipment. In washer-limited mill examples, we calculated that membrane systems can reduce the annual operating cost for a 7% production increase by 91%. Similarly, in evaporator-limited mill examples, membrane systems can reduce the annual operating cost for a 7% production increase by 86%. These results indicated that membrane systems make a production increase significantly more feasible for these equipment-limited mills.
Journal articles
Conversion of paper-grade pulp from rice straw into dissolving pulp, TAPPI Journal June 2025
ABSTRACT: About 1,165 million metric tons of rice straw is generated every year worldwide, which can be a good source for the circular bioeconomy. In this research paper, the paper-grade pulp from rice straw was converted to dissolving-grade pulp by fractionation in a biorefinery initiative. Rice straw was cooked at an optimum condition of 8% potassium hydroxide (KOH) charge for 120 min at 150°C and produced a pulp yield of 47.2% with a kappa number of 18.5. Subsequently, D0(EP)D1 bleaching was carried out for the produced pulp, and the brightness of the pulp reached to 82.4%. From the black liquor, 16.5% of the lignin and 11.9% of the hemicellulose were isolated for producing biobased products and chemicals, and then the spent liquor was used for soil amendment. The bleached pulp was fractionated in a Bauer McNett fiber classifier. The pulp fibers retained on 16-, 30-, and 50-mesh screens were used as a longer fiber fraction pulp, and pulp fibers retained on 100- and 200-mesh screens were used as a shorter fiber pulp. The longer and shorter fiber fraction pulps were analyzed for cellulose, R10, pentosan, and viscosity. The long fiber fraction pulps were characterized by higher cellulose (88.2% vs. 83.1%) and lower pentosan (11.3% vs. 13.0%) content than the shorter fiber fraction pulps. The longer fiber fraction was further treated with cold KOH to remove residual hemicellulose. The KOH extraction reduced pentosan content in pulp to 6.3% and increased á-cellulose content to 91.3%. The short fiber fraction was converted to monomeric sugars using cellulase enzymes with varying reaction time, temperature, and consistency. The efficiency of cellulase activity was assessed through glucose yield and residual dry weight. A temperature of 45°C, 5.0 pH, 5% consistency, and 6 filter paper units/gram (FPU/g) o.d. pulp resulted in maximum sugar conversion of 85.7%.