Kraft Cellulose Research Articles

CARBOXYLATED NANOCELLULOSE OBTAINED THROUGH ULTRASONICATION USING AN ALTERNATIVE ACID MIXTURE SOLVENT

The growing concern for a safer chemical industry has spurred research towards replacing strong acid solvents, because of the significant hazards they cause, such as issues related to effluent treatment and high corrosiveness. In the production of nanocellulose, sulfuric acid stands out as an example, being highly corrosive, yet widely used. This study aimed to investigate a more ecological acid mixture solvent, specifically comprising hydrochloric acid (HCl) and citric acid (CA), for obtaining carboxylated nanocellulose from kraft cellulose pulp. Distinct methodologies were employed based on three different durations, corresponding to each methodology (30 minutes, 60 minutes, and 90 minutes). FTIR analysis confirmed the occurrence of chemical modification. Among these methodologies, ultrasonication for 60 minutes yielded the best carboxylated nanocellulose, as determined through morphological analysis, with an average diameter of 8.4 nm and an average length of 123 nm. X-ray diffraction (XRD) revealed a decrease in crystallinity; however, both kraft pulp and carboxylated nanocellulose exhibited the cellulose Iβ allomorph. This surface modification paves the way for incorporating new functional properties into the design of composites, hydrogels, Pickering emulsions, drug delivery systems, food packaging, and biofilms.

OPTIMIZATION OF A PHOTOCATALYTIC PROCESS FOR REMOVAL OF PHENOLIC COMPOUNDS FROM WASTEWATER GENERATED IN THE PRODUCTION OF CELLULOSE FROM PINUS RADIATA AND EUCALYPTUS GRANDIS WOOD

This study aimed to improve the sustainability of the kraft pulp production process by recovering Pinus radiata and Eucalyptus grandis wastewater generated during the bleaching process. The effluents were obtained from the first alkaline extraction stage (E0) of the ECF bleaching sequence used to produce white Kraft cellulose, considering that this stage is where the highest contamination by phenolic compounds occurs and the effluent exhibits an intense color. A photochemical oxidation system, utilizing TiO2/S2O82-/UV, was implemented to generate in situ two highly oxidizing radical species, with high redox potential, a hydroxyl radical (HO• 2.8 eV ) and a sulfate radical (SO4•- 2.5-3.1 eV), which promote rapid degradation of contaminants. To obtain the optimal response, we employed the 2n model to construct a matrix of 15 experiments, utilizing the Box-Behnken design. According to the experimental variables studied, phenolic compounds were completely removed from the Eucalyptus effluent (0.0312 min-1) and 80% of them were removed from the pine effluent (0.0102 min-1), at pH 5.0 with 0.6 gL-1 of persulfate and 1.0 gL-1 of titanium dioxide. Under these conditions, the bioavailability of effluents from Pinus radiata and Eucalyptus grandis increases from 0.16 and 0.26 to 0.90, after the treatment. The excellent bioavailability of the effluents obtained after the treatment demonstrates that the process used is efficient in recovering wastewater from the pulp industry and that the treated water could be reused in the same process or returned to the ecosystem, without harming the environment.

Bubble Effect Phenomenon in Modern Transformer Insulation Systems Using Aramid-Based Materials and Alternative Insulating Liquids

One of the possible causes of transformer failures is high moisture in the winding insulation system. In an extreme case, when the critical temperature is exceeded, a sudden release of water vapor from the transformer insulation, called the bubble effect, can occur. This article analyzes the initiation temperature of the bubble phenomenon in various solid insulation materials (Kraft cellulose paper and aramid-based high-temperature papers such as Nomex® 910 and Nomex® 926) immersed in two electro-insulating liquids (mineral oil and Midel 7131 synthetic ester). The initiation temperature of the bubble effect depends mainly on the moisture content of the solid insulation, but it was found to be slightly lower for high-temperature materials than for cellulose. However, after taking into account the differences related to uneven water absorption of the tested materials, the differences in the initiation temperature of individual solid materials are very small. Synthetic ester, compared to mineral oil, slightly increases the bubble initiation temperature, regardless of the solid material used.

Optimization of anaerobic digestion and solubilization of biosludges from the kraft cellulose industry using thermal hydrolysis as pretreatment

The management of secondary sludge from aerobic treatment of effluents from the cellulose industry is a current problem. The usual ways of disposal do not provide added value to the waste as they assume an economy based on “take-make-waste” (linear economy). In this work, thermal hydrolysis (TH) and anaerobic digestion (AD) are proposed to valorize this biosludge. Based on a Doehlert experimental plan, a response surface methodology (RSM) defined by seven different TH conditions is proposed. After TH, biomethanation potential (BMP) tests were performed to evaluate the AD possibilities. The TH conditions cover a temperature range between 125 °C and 205 °C and a reaction time from 15 min to 45 min. The TH process was successful in enhancing the bioavailability of the waste, increasing the concentration of soluble organic matter quantified by chemical oxygen demand of the soluble fraction (CODs), and decreasing the concentration of volatile suspended solids (VSS). However, response surfaces performed for CODs and VSS revealed the existence of optimums, which demonstrated the adverse effects of the more severe TH conditions. Organic matter solubilization was confirmed by microscopic observations. The amount of suspended organic matter after TH is reduced by two to three times compared to the untreated value. The subsequent BMP of the hydrolyzed waste increases between 100% and 220% compared to the untreated condition, wich had a BMP value of 84 NmL CH4 gVS−1. The response surface determined for the BMP reveals the presence of a maximum point of methane production at 202 °C for 31 min, which differs from the maximum CODs value observed at 196 °C for 40 min.

Possible alternatives for using kraft lignin as activated carbon in pulp mills – a review

Abstract The uses of kraft lignin (KL), obtained from the black liquor (BL) in the pulping process, allow the production of activated carbon (AC), a product with high added value in the pulp mill. The AC can be used in three different sectors in a cellulose pulp mill: sectorial treatment of the cellulosic pulp bleaching filtrates; wastewater treatment; and in the treatment of water received by the mill. Thus, this article considers the steps in the production of AC, their types, and the advantages and challenges of its use in the kraft cellulose pulp mill as well as in other industries.

Endo-Exoglucanase Synergism for Cellulose Nanofibril Production Assessment and Characterization.

A study to produce cellulose nanofibrils (CNF) from kraft cellulose pulp was conducted using a centroid simplex mixture design. The enzyme blend contains 69% endoglucanase and 31% exoglucanase. The central composite rotational design (CCRD) optimized the CNF production process by achieving a higher crystallinity index. It thus corresponded to a solid loading of 15 g/L and an enzyme loading of 0.974. Using the Segal formula, the crystallinity index (CrI) of the CNF was determined by X-ray diffraction to be 80.87%. The average diameter of the CNF prepared by enzymatic hydrolysis was 550-600 nm, while the one produced by enzymatic hydrolysis and with ultrasonic dispersion was 250-300 nm. Finally, synergistic interactions between the enzymes involved in nanocellulose production were demonstrated, with Colby factor values greater than one.

Kinetic study and real-time monitoring strategy for TEMPO-mediated oxidation of bleached eucalyptus fibers

The present work aims at glimpsing the rate-determinant process parameters of TEMPO-mediated oxidation of bleached kraft cellulose for developing kinetic models and real-time monitoring tools. This may contribute to the scaling up of this reaction, frequently used as precursor of the production of cellulose nanofibers. For this, the effect of temperature, TEMPO and NaBr contents, and surface area of the fibers was assessed by means of a total experimental batch of 18 combinations, monitoring the carboxyl content (CC) of the samples and the NaOH consumption during oxidation. The obtained data was used to calculate the kinetic constant as a function of the conditions, as well as correlating the CC with the NaOH consumption, obtaining a strong linear correlation between these parameters. It was found that similar correlations could be used regardless process conditions, except for the case of TEMPO, which was found to protect the fibers from depolymerization and, thus, having different behavior at increasing TEMPO contents. Overall, the obtained results in the present study reveal the suitability of upscaling TEMPO-mediated oxidation, as well as having a deeper understanding on how the key parameters involved in the reaction affect the reaction path and, thus, contributing to the industrial deployment of oxidized cellulose and nanofibers.

Bacterial diversity in aerated facultative lagoon treating kraft cellulose effluent with bioaugmentation

The microbiological diversity was evaluated in an aerated facultative lagoon system with organic loading rates of 0.2 and 0.6 kgCODm-3d-1 treating effluent from the kraft pulp industry for bioaugmentation purposes. Samples were taken from a laboratory-scale lagoon at steady state treating kraft pulp effluent and operated with two different rates for 120 days. The analysis was performed by 16S rDNA sequencing. The autochthonous bacteria were identified through statistical similarity obtained from the NCBI-BLAST database. The lagoon performance was assessed based on the removal efficiency of biochemical oxygen demand (94% and 80%), chemical oxygen demand (51% and 44%), total organic carbon (49% and 41%), lignin-derived compounds (13% and 27%), turbidity (94% and 87%), for the low and high rates used respectively. Color and TPC were not significantly removed during the biological treatment of the industrial matrix. In the biomass samples collected at a steady state, 9 and 12 species of bacteria were identified at the applied rates. The species Bacillus cereus, Bacillus thuringiensis, and Paenibacillus glucanolyticus found in this matrix presented significant removal of the parameters in the kraft effluent. The three referred species show great promise in the removal of specific parameters in an AFL biological treatment system using bioaugmentation.

Composition optimization and characterization of combustible cartridge cases with polyvinyl acetate (PVAc) as a binder

Combustible cartridge case samples composed of nitrocellulose (NC), polyvinyl acetate (PVAc), kraft cellulose (KC), dibutyl phthalate (DBP) and diphenylamine (DPA) were prepared to study their structures and chemical and mechanical properties. Taguchi’s experimental design method was used to design the experimental formulations. First, simultaneous thermogravimetry-differential scanning calorimetry (STA TG-DSC), scanning electron microscopy (SEM), Brunauer–Emmett–Teller analyser (BET), bomb calorimeter (BC), vacuum stability tester (VST) and a tensile testing machine (TTM) were employed to analyse the thermochemical characteristics, structure, explosion heat, chemical stability and compatibility, and mechanical strength of all formulated samples. Based on the analysis results, the weight loss of the combustible cartridge case sample obtained by the TG experiment was chosen as the quality characteristic. The results of the Taguchi analysis indicated that the optimal parameter combination was an NC/KC weight ratio of 80:20, an NC/PVAc weight ratio of 85:15, an additional DPB of 3.5 wt.% and a density of 1.25 g/cm3. The results of the chemical stability and compatibility test, explosion heat test and mechanical strength test show that the test samples prepared with the optimal parameter combination can meet the requirements of combustible cartridge cases. Furthermore, the combustion performance of the combustible cartridge case sample prepared with the optimal formula was measured by a high-temperature combustion furnace (HTCF) and burning rate measurement device (BRM). The experimental results indicated that the autoignition temperature and ash content were 231 °C and 0.28%, respectively. In addition, the burning rate increased with increasing combustion chamber pressure but was lower than that of ordinary gun propellants at the same pressure. These combustion characteristics can meet the quality requirement of combustible cartridge cases. Finally, an actual combustible cartridge case was prepared and verified. The result of the performance verification test indicated that the average ash content was 0.30%, which was similar to that of the previous test samples and met the quality requirement.

Bio-based films/nanopapers from lignocellulosic wastes for production of added-value micro-/nanomaterials.

The growing demand for products with lower environmental impact and the extensive applicability of cellulose nanofibrils (CNFs) have received attention due to their attractive properties. In this study, bio-based films/nanopapers were produced with CNFs from banana tree pseudostem (BTPT) wastes and Eucalyptus kraft cellulose (EKC) and were evaluated by their properties, such as mechanical strength, biodegradability, and light transmittance. The CNFs were produced by mechanical fibrillation (after 20 and 40 passages) from suspensions of BTPT (alkaline pre-treated) and EKC. Films/nanopapers were produced by casting from both suspensions with concentrations of 2% (based in dry mass of CNF). The BTPT films/nanopapers showed greater mechanical properties, with Young's modulus and tensile strength around 2.42 GPa and 51 MPa (after 40 passages), respectively. On the other hand, the EKC samples showed lower disintegration in water after 24 h and biodegradability. The increase in the number of fibrillation cycles produced more transparent films/nanopapers and caused a significant reduction of water absorption for both raw materials. The permeability was similar for the films/nanopapers from BTPT and EKC. This study indicated that attractive mechanical properties and biodegradability, besides low cost, could be achieved by bio-based nanomaterials, with potential for being applied as emulsifying agents and special membranes, enabling more efficient utilization of agricultural wastes.

Microbiological diversity in an aerated lagoon treating kraft effluent

The microbiological diversity of cultivable bacteria was analyzed in an aerated facultative lagoon. The removal of specific compounds and measures of pollutant load was evaluated with isolated native bacteria, selected and identified in kraft cellulose effluent. The system was operated with an organic loading rate of 0.2 kgCODm-3d-1 for 60 days. Analyses of the fluorescence excitation-emission matrix, acute ecotoxicity, and microbiology were performed. Bioaugmentation tests were done to emphasize the removal of color, using promising species. The removals of biochemical oxygen demand, chemical oxygen demand, and total organic carbon in AFL were 94%, 51%, and 41%, respectively. Regarding color, removal was up to 4%, and the total phenolic compounds were not removed through biological treatment. The treatment also decreased turbidity by 94% and lignin derivatives by 12%. The bacteria identified through NCBI-BLAST and statistical similarity totaled 9 species in the cellulose effluent, three of which have the potential for color treatment: Bacillus cereus, Bacillus thuringiensis, and Paenibacillus sp. The Bacillus cereus combined with biomass removed color (69%), total phenolic compounds (37%), and compounds derived from lignin (53%). These species are promising for removing specific parameters combined with biomass from biological AFL treatment systems.

Wood delignification with aqueous solutions of deep eutectic solvents

The development of a sustainable wood fractionation has been a goal for the pulp and paper industries to develop a bioeconomy. The use of green solvents, in particular deep eutectic solvents (DES) has been explored to accomplish such goal. This work unveils the potential of DES aqueous solutions (at 50 wt% water content) as green solvents for the Eucalyptus globulus Labill. wood delignification. Aqueous solutions of propionic acid:urea - PA:U (2:1), urea:choline chloride - U:Ch[Cl] (2:1), lactic acid:choline chloride - LA:Ch[Cl] (10:1) and p-toluenesulfonic acid:choline chloride - PTSA:Ch[Cl] (1:1) were investigated. The delignification process was assisted by the addition of mineral (H2SO4 and HCl) or organic (PTSA) acids to efficiently promote wood matrix disruption and further lignin extraction. This process enabled solid pulp and lignin as separated fractions, which were characterized by analytical, optical and spectrometric methods. The influence of each DES on the morphology of cellulose fibers in solid pulp and the chemical structure of isolated lignin fractions was evaluated. The best system allowing delignification while preserving the cellulose fibers (comparable to Kraft cellulose pulp) and lignin structure was PA:U (2:1) aqueous solution with 25 wt% PTSA. A mild wood delignification process (363.15 K for 8 h) using this DES allowed to obtain a cellulose pulp yielding 59.50 ± 0.51 wt% of the initial wood mass and containing only 3.86 ± 0.10 wt% residual Klason lignin content. This innovative approach led to 80.64 wt% lignin extraction from E. globulus wood at mild conditions showing its potential for industrial application. Furthermore, 40.73 wt% of the initial lignin was recovered from DES liquor by a simple precipitation with water.

3D fiber models to simulate and optimize tissue materials

Tissue materials development using 3D computational tools to predict the influence of the combination of different fibers can be employed in the design of innovative tissue products and furnish optimization. Fibrous materials can be designed using different 3D fiber models for each type of fibers, detailed to the point where the wall fiber thickness, fiber lumen, and collapse degree are considered and presented in this work. Eucalyptus, Pinus, and Picea kraft cellulose pulp fibers were selected because they are representative of differentiated fiber types. The fiber morphological measurements were obtained using two methods: one uses the fibers in suspension, without restraints, and the other uses a capillary fiber alignment. The results indicate good repeatability for both methods but differences of 14% for fiber length weighted in length, 2% for fiber width, 11% for coarseness, 35% for curl, and 88% for fines content. Scanning electron microscopy images were used to identify the fiber dimensions inside the tissue structure. Four different types of fiber models for eucalyptus fibers, with different fiber wall thickness and lumen dimensions, were presented and used to predict 3D computational fibrous structures.

Efficient application of cellulose pulp and paper production wastes to produce sustainable construction materials

The mechanical and physical properties of the composites developed from dregs, grits, and lime mud of the Kraft cellulose and paper production process (55–75%), concrete waste (10–25%) and lime production waste (0–25%), far exceeded the demands of Brazilian standards for bricks, blocks, and road-base construction materials. The study of the developed composites structure by XRF, XRD, SEM, EDS, and LAMMA methods demonstrated that new mainly amorphous formations were responsible for all attained properties. The industrial application of these construction materials would introduce excellent efficiency from an economic and environmental points of view.

Moving bed biofilm reactor for treatment of Kraft pulp effluent with high organic load rate

The pulp industry uses more than 40 m3 of water per ton of pulp produced, generating high effluent flows. In general, it presents high concentrations of organic matter, color and ecotoxicity. The most widely used effluent treatment systems in the pulp industry are biological, including moving bed biofilm systems that are efficient in removing biodegradable organic matter. This work evaluated the removal of organic matter, total phenolic compounds, color and lignin derivatives in the treatment of Kraft cellulose effluent using the moving bed biofilm reactor (MBBR), and also evaluated the support media biofilm development by solid analysis and scanning electron microscopy. The parameters evaluated during treatment were: BOD5, COD, color, total phenolic compounds, lignin derivatives, and solids, with tests performed on organic loads from 0.7 and 8.9 kgCOD m-3 d-1. Organic matter removal remained stable, being over 80% to BOD5 and over 42% to COD. The color and the total phenolic compounds were removed up to approximately 7 and 28%, respectively. Over 19% removal of derivatives of lignin compounds was observed in both organic load rates. In the MBBR, biofilm was confirmed and enabled this biological system to treat the cellulose effluent in a stable way.

One-step preparation of bilayered films from kraft lignin and cellulose acetate to mimic tree bark

This contribution presents the development of a dry-cast method for the one-step preparation of bio-based films from wood polymers that mimic the bilayered structure of tree bark, the natural protective layer of the tree. In a simplified view, natural bark can be considered as the superposition of an external homogeneous and non-porous layer (outer bark) and a porous substructure layer (inner bark). This work is a first step for the future development of bio-based biomimetic wood coatings. The film had a bark-like appearance and its total density, bulk density and porosity were similar to values measured in natural bark. Furthermore, the structural characteristics of the studied film, namely specific surface area (BET) and pore size distribution, as well as the performance of the water adsorption ability were investigated and discussed.

Purification of Kraft cellulose under mild conditions using choline acetate based deep eutectic solvents

Novel choline acetate based deep eutectic solvents (DESs) solubilize hemicellulose up to 45 wt% at 80 °C. A PoC test on Kraft cellulose illustrates the cellulose/hemicellulose separation.

Metal Phthalocyanines as Catalyst Precursors of Metallated Carbon Nanotubes.

The addition of nanoparticles to cellulose paper can improve its mechanical strength, chemical stability, biocompatibility and hydrophobic properties. Silica nanoparticles are known to be inert, hydrophobic, biocompatible, biodegradable and have a good distribution being deposited on surfaces. The main characteristics of 20 nm SiO2 nanoparticles are good chemical and thermal stability with a melting point of 1610-1728°C, a boiling point of 2230°C with a purity of 99.5%. To carry out the hydrophobization of paper based on Kraft cellulose and on cellulose obtained from soybean husk with 20-nm size SiO2 nanoparticles and to study hydrophobicity, morphology and topography of the prepared composites. Few relevant patents to the topic have been reviewed and cited. The ground and roasted soybean husk was treated with a NaOH, washed and dried. Hydrophobization of paper was carried in aqueous medium by SiO2 addition in weight ratios "paper-SiO2 " of 0.01-0.05 wt.%, stirring, filtration and drying. The obtained cellulose sheet composites were characterized by Scanning Electron Microscopy (SEM), Transmisión Electron Microscopy (TEM), FTIRspectroscopy, Mullen proofs of hydrophobicity, and contact angle measurements. The mechanical properties of paper nanocomposites (tensile strength and compression) increased considerably by varying the concentrations. The tensile strength increased by 41-46% and the compressive strength increased by 55-56%. The existence of fiber nanofoils, good adhesion of 20-nm SiO2 nanoparticles to the paper surface, and their homogeneous distribution were observed. Cellulose was successfully obtained from soybean husk, applying the alkaline-based extraction method. A good reinforcement of cellulose fibers is observed due to the outstanding characteristics of the silicon dioxide nanoparticles.

Hydrophobization of Kraft-type Cellulose and Microfiber Cellulose Obtained from Soybean Husk in Ultrasonic Field.

The addition of nanoparticles to cellulose paper can improve its mechanical strength, chemical stability, biocompatibility and hydrophobic properties. Silica nanoparticles are known to be inert, hydrophobic, biocompatible, biodegradable and have a good distribution in being deposited on surfaces. The main characteristics of 20 nm SiO2 nanoparticles are good chemical and thermal stability with a melting point of 1610-1728°3C, a boiling point of 2230°C with a purity of 99.5%. To carry out the hydrophobization of paper based on Kraft cellulose and on cellulose obtained from soybean husk with 20-nm size SiO2 nanoparticles and to study hydrophobicity, morphology and topography of the prepared composites. The ground and roasted soybean husk was treated with a NaOH, washed and dried. Hydrophobization of paper was carried in aqueous medium by SiO2 addition in weight ratios "paper-SiO2" of 0.01-0.05 wt.%, stirring, filtration and drying. The obtained cellulose sheet composites were characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), FTIRspectroscopy, Mullen proofs of hydrophobicity, and contact angle measurements. The mechanical properties of paper nanocomposites (tensile strength and compression) increased considerably by varying the concentrations. The tensile strength increased by 41-46% and the compressive strength increased by 55-56%. The existence of fiber nanofoils, good adhesion of 20-nm SiO2 nanoparticles to the paper surface, and their homogeneous distribution were observed. Cellulose was successfully obtained from soybean husk, applying the alkaline-based extraction method. A good reinforcement of cellulose fibers is observed due to the outstanding characteristics of the silicon dioxide nanoparticles.

Esterification optimization of cellulose with p-Iodobenzoyl chloride using experimental design method

The synthesis and characterization of kraft cellulose p-iodobenzoate is presented in this paper. The ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) as a reaction medium for the synthesis of cellulose p-iodobenzoate by homogeneous esterification of dissolved kraft cellulose with p-iodobenzoyl chloride. The degree of substitution (DS) of cellulose ester was calculated from the 1H-NMR spectra. In first time, the chemical structure and properties of the obtained products were characterized by FT-IR and NMR spectroscopy. Cellulose p-Iodobenzoates ester with a DS in the range from about 0.18 to 2.05 were accessible under mild conditions. The DS of cellulose ester increased with the increase of the molar ratio of iodobenzoyl chloride/anhydroglucose unit in cellulose, reaction time, and reaction temperature. In second time, the Response Surface Methodology (RSM) that was based on a Box-Behnken design was used for optimize the esterification of cellulose. The effects of three parameters were investigated: (X1) number of mole of reactant, (X2) reaction temperature, and (X3) reaction time. The Analysis of variance (ANOVA) indicated that linear terms of (X1), (X2), (X3), the quadratic term of (X12) and (X32) have a significant effect (p < 0.10 with a 90% confidence level) on DS of cellulose ester. The fitted model indicated that the optimum reaction conditions to esterification of cellulose were: number of mole 7,49 mol, reaction temperature 100 °C, and 217,50 min for reaction time, respectively. Under these conditions, the numerical estimation of DS was 2,051. This result was experimentally validated obtaining a difference of 2.7% DS of cellulose ester, with respect to simulated values.