Bleached Pulp Research Articles

Organic acid fractionation of hardwoods planted in social forestry

Abstract Trema orientalis and Trewia nudiflora are the fastest rotation trees (3–4 years’ rotation) in Bangladesh, and experimentally planted in social forestry in Gazipur district. Biorefinery is the most cited topic in research recent era in order to established circular bioeconomy. In established a biorefinery initiative, both species were fractionated into pulp, lignin and hemicellulose by formic acid (FA) treatment at atmospheric conditions. After alkaline peroxide bleaching of FA treated pulp, the yield was 47.0 % and 41.0 % with α-cellulose of 82.39 % and 81.61 %, and residual pentosan content of 9.26 % and 11.13 % for T. orientalis and T. nudiflora, respectively. The brightness of the pulps was 84.5 % and 85.0 %. Cold alkali extraction of the bleached pulp increased α-cellulose to 92.36 % and 91.29 % which was suitable for cellulose derivatives. Lignin was separated from the spent liquor by adding water. The FA lignin from hardwood replaced 20 % phenol in phenol-formaldehyde resin preparation without sacrifice of shear strength. The lignin separated FA liquor contains mainly pentose sugars, which was subsequently converted to furfural with a yield of 41.39 % and 41.72 % at 170 °C using 0.1 % H2SO4 catalyst from T. orientalis and T. nudiflora, respectively.

Green oleogels based on elm pulp cellulose nanofibers: effect of the nanofibrillation pre-treatment on their thermo-rheological behavior

Sustainable lubricating oleogels were obtained based on elm (Ulmus minor Mill.) pulp cellulose nanofibers in castor oil. Before their nanofibrillation, two samples of the same bleached pulp were subjected to two different pre-treatments, either mechanical PFI (Paper and Fibre Research Institute) refining or chemical TEMPO-mediated oxidation. Their effect on the oleogels’ viscous flow and oscillatory shear behaviors was determined at different temperatures. Very pronounced differences were observed between these oleogels. The oleogel from the chemically-pretreated nanofibers showed evidences of being much more sensitive to both temperature and large shear deformations. Hence, its shear modulus underwent a very remarkable decay of 95.8% when subjected to a non-linear stress value of 100 Pa for 30 min. In turn, under the same conditions, a decay of only 41.4% was observed for the oleogel based on the nanofiber from the mechanically-pretreated nanofibers.Graphical abstract

Enzyme-assisted dewatering and strength enhancement of cellulosic fibers for sustainable papermaking: A bench and pilot study

Water removal during paper manufacturing is of primary importance to production rate and cost efficiency for the pulp and paper industry. It is crucial to develop methods to reduce energy consumption by increasing the percent solids in the paper web entering the dryers from the presses. This research aimed to develop a fundamental understanding of the effect of bio-chemo-mechanical pretreatments on a bleached softwood fiber matrix and evaluate the impact on the percent solids of the paper web after pressing. Experiments included enzymatic, refining, and cationic polymer pretreatments on the bleached softwood pulps, followed by laboratory papermaking and determining the equilibrium moisture content (EMC) after pressing and the pulp and paper properties. The combined effect of mild refining, controlled enzymatic pretreatments, and cationic strength aids proved to enhance the water removal during wet pressing (up to 35 % reduction) and increase paper strength (up to 60 % increase). The results of increased solids after pressing were used to calculate the potential reduction in drying energy during paper manufacturing. Energy savings of around 10 % for paper drying could be achieved through fiber matrix modification by bio-chemo-mechanical pretreatment. Enzymatic pretreatments have previously been conventionally applied before refining as an energy-saving method. However, this research shows that synergistic actions of enzymes added after refining modify the fibers and create the optimal conditions for enhancement in drainage, press dewatering, and paper properties.

Zeolitic imidazolate framework-67 enabled cellulosic paper for efficient particulate matter capture

The combination of functional zeolitic imidazolate frameworks (ZIFs) with suitable substrates is promising for the preparation of advanced filtering materials. In this study, the bleached kraft softwood pulp (NBKP) was composited with ZIF-67 particles via an in situ growth method to fabricate functional paper. Enabled by the traditional papermaking process, ZIF-67 crystals were uniformly and tightly anchored on cellulosic fibers in a facile and economic way. The introduction of ZIF-67 boosted the mechanical performances of the composite paper owing to the presence of electrostatic interactions and hydrogen bonds. Meanwhile, the resultant paper presents hierarchical porous structure with a large specific surface area of 327.07 m2·g−1. The filters with hierarchical pore structure will provide a complex tortuous channel for passing particulates, which can increase the frequency of effective collision between filters and particulates. Air filtering tests demonstrated that the ZIF-67 entrapped paper has superior particle removal efficiency with a low pressure drop and a large dust holding capacity. The optimal ZP-3 sample displayed removal efficiencies of 98.52 % for PM2.5 and 99.00 % for PM10. Meanwhile, filtration quality factors were calculated to be 0.15 (PM2.5) and 0.17 (PM10), respectively. The filter also has good antibacterial activity. In addition, ZP-x composite paper is easy to regenerate and possesses good reusability. The high-efficient ZP-x filter will have potential applications in fields of air purification.

A Versatile Shaping Method of Very-High Loading Porous Solids Paper Adsorbent Composites.

Owing to their high porosity and tunability, porous solids such as metal-organic frameworks (MOFs), zeolites, or activated carbons (ACs) are of great interest in the fields of air purification, gas separation, and catalysis, among others. Nonetheless, these materials are usually synthetized as powders and need to be shaped in a more practical way that does not modify their intrinsic property (i.e., porosity). Elaborating porous, freestanding and flexible sheets is a relevant shaping strategy. However, when high loadings (>70wt.%) are achieved the mechanical properties are challenged. A new straightforward and green method involving the combination softwood bleached kraft pulp fibers (S) and nano-fibrillated cellulose (NFC) is reported, where S provides flexibility while NFC acts as a micro-structuring and mechanical reinforcement agent to form high loadings porous solids paper sheets (>70wt.%). The composite has unobstructed porosity and good mechanical strength. The sheets prepared with various fillers (MOFs, ACs, and zeolites) can be rolled, handled, and adapted to different uses, such as air purification. As an example of potential application, a MOF paper composite has been considered for the capture of polar volatile organic compounds exhibiting better performance than beads and granules.

Characterization of spray dried cellulose nanofibrils produced by a disk refining process at different fineness levels

Three types of wood pulp feedstocks including bleached softwood kraft, unbleached softwood kraft and old corrugated containers were disk refined to produce cellulose nanofibrils at different fineness levels ranging from 50 to 100%, and the resulting aqueous suspensions of cellulose nanofibrils were spray dried. The spray drying experiments were carried out to examine different processing conditions for the different CNF feedstock types and fines level at various suspension concentrations to produce dry samples with free-flowing powder morphologies. The fineness levels and solids contents of CNF suspensions were set to 80% or more and 1.8% or less, respectively. If the solids content of the CNF solutions was high and the fibrillation level was low, plugging was experienced in the spray head because of the high viscosity of the suspensions, resulting in production of poor-quality powders. In terms of reduction in processing energy, even if the CNF suspension solids content was increased to 1.5 wt.%, the powder quality and the production yields were excellent. It was confirmed that high-quality powder under 20 µm were produced at a 90% fibrillation level of all CNF feedstocks. The resulting dry CNF powders were characterized to determine particle size distributions and morphological properties via a scanning electron microscope and a laser diffraction particle size analyzer. The particle sizes were smaller at higher fibrillation levels and lower solids content of the CNF suspensions. The CNF suspension derived from bleached kraft pulp, the average particle size decreased by 43% and 33% with the lowered solids contents from 1.8 to 1%, and the increased fineness levels from 80 to 100%, respectively.

Analysis of the commercial eucalyptus plantation sector in Uruguay from a macroeconomic perspective

The Uruguayan forest sector has developed based on commercial pine and eucalyptus plantations. This process has been based on the installation of vertically integrated companies, with foreign capital and some local capital, investment funds and medium and small industries. In addition to these groups, there are contractor companies in which several of the activities of the primary sector are outsourced, as well as some of the industry. Investment attraction factors are diverse and related not only to productive conditions, e.g., growth rates, but also to institutional conditions, e.g., macroeconomic stability. With the development of the forest sector, there is currently a preponderance of eucalyptus plantations over pine plantations. This characteristic has implications in terms of the products to be obtained and, therefore, the industries to be developed, and the markets to be accessed. The presentation analyzes the evolution of the participation of the forest sector in Uruguay's macroeconomy, considering its share in the country's exports as well as in international trade, with emphasis on the products obtained from eucalyptus plantations. The scope and limitations of the available data for Uruguay are considered. Finally, the importance of including the value of ecosystem services provided by the forest in the traditional macroeconomic valuation is discussed. Results show that Uruguay has an important participation in non-coniferous wood markets. According to FAO data, in 2022, Uruguay's production ranked 8th among non-coniferous pulpwood producing countries, after Chile, up one place from the previous year. The same year Uruguay ranked 10th in terms of production of bleached wood pulp. Furthermore, it is expected that the wood pulp will increase with the new operations of the third pulp mill. Furthermore, cellulose pulp ranked 3rd among Uruguay's export products in 2022, after beef and soybeans, and 2nd in the previous year. The results of this research are of interest to potential investors in the Uruguayan forest sector as well as to policymakers. Potential investors in the Uruguayan forest sector may find insights into the industry's growth potential. Policymakers can use this information to make informed decisions that support the development and regulation of the sector for the benefit of both the economy and the environment.

Photosensitive cellulosic materials based on a covalently grafted phenosafranin-modified silsesquioxane analog for bactericidal applications

Light-triggered antimicrobial cellulose surfaces were obtained by the immobilization of a photosensitive phenosafranin dye (PSF) in a hybrid organic–inorganic silsesquioxane polymer applied on handsheets prepared from a standard bleached softwood pulp. These coatings were deposited by polycondensation of methyltriethoxysilane and an alkoxysilyl derivative of phenosafranin (TESPSF) obtained by the thiolene addition reaction and coupling of the succinic anhydride derivative with a primary amine group of PSF. TESPSF and coatings were characterized by advanced techniques in terms of chemical structure (1H, 13C, 29Si NMR, MS, ATR-IR), surface properties (SEM, EDX, water contact angles), and optical properties (UV, reflection light intensity, ISO brightness). The light-induced antimicrobial activity of sheets of paper coated with new materials showed the inhibition of the growth of the bacteria Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC 8739. The cytotoxicity studies of modified cellulose surfaces were performed using erythrocyte lysis assays under both dark and light conditions exhibited no toxicity on erythrocytes. Thus, the new material did not reveal harmful effects on erythrocytes, regardless of the presence and absence of light.

Identification of tropical wood species in paper: a new chemotaxonomic method based on extractives

Abstract The European Deforestation Regulation 2023/1115 (EUDR) prohibits trading of wood and wood products obtained from illegal logging on the EU market. While the identification of solid wood via anatomy, chemistry and genetics has already been established, there is a lack of identification methods for pulp and paper that complement anatomy. This publication presents a newly developed chemotaxonomic method for identifying mixed tropical hardwood (MTH) species in pulp and paper products based on their extractives analyzed with thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The measured data was processed and compared to identify marker substances and was then merged into a fingerprint database for identifying MTH species in paper of unknown composition. As database references, fully bleached kraft pulps were produced from 38 anatomically identified wood samples and then cryo-ball milled and extracted successively with n-hexane and acetone. The results show that the remaining wood extractives generated from bleached pulps are specific enough to find chemical relevant marker substances to detect MTH species. As chemical composition and anatomy are independent characteristics of wood, this paper makes a completely independent method available, which potentially improves the screening for Convention on International Trade in Endangered Species of Wild Fauna and Flora (CITES) protected species.

Kraft pulp viscosity as a predictor of paper strength: Its uses and abuses

For bleached kraft pulps, two factors govern paper strength: the individual fiber strength, and the bond strength that adheres the individual fibers together in the paper matrix. Inherent fiber strength is related to the length of the carbohydrate polymers, also known as the degree of polymerization (DP). Average DP (DP) is inferred by performing pulp viscosity measurements. Under certain circumstances during kraft pulping and bleaching, the average polymer lengths can be shortened, resulting in lower pulp viscosity, and may indicate fiber damage. Fiber damage typically manifests itself as a reduction in tear strength for well-bonded handsheets. This paper will review the literature on how pulp viscosity can predict paper/fiber strength and how it can be used as a diagnostic tool. It can be a means to monitor pulp quality during pulping and bleaching, as well as to alert when such operations approach a critical threshold. However, viscosity losses must be carefully and judiciously analyzed. Like most diagnostic tools, viscosity measurements can be misused and abused, which can lead to incorrect inferences about intrinsic fiber strength. This review will also cover these misuses. The overall goal is to provide the papermaker a better understanding of what pulp viscosity is, how it correlates to potential sheet strength, and what its limitations are. It will be illustrated that when pulp viscosity drops below a critical value, it will indicate an appreciable deterioration in the paper’s tear and tensile strength.

Thermal-degradation characteristics of mechanically nanofibrillated bleached pulps from hardwood and softwood

Nanofibrillated cellulose (NFC) consists of ultrafine cellulose structures in which the fibrils can have widths in the range from about 5 to 100 nm. NFC has been studied and developed in the paper industry, using bleached pulp from wood as the raw material. One of the issues in the application of NFC is their heat resistance to thermal degradation. The production process of NFC results in a decrease in their pyrolysis temperature during the nanofibrillation of bleached pulp; however, the details behind the reason and mechanisms are still unclear. In this study, NFC was prepared from bleached hardwood and softwood pulp by mechanical nanofibrillation using a grinder, and the pyrolysis behavior was investigated. For both bleached pulps, a decrease in the pyrolysis temperature was observed after nanofibrillation. The results suggest that the decrease in the pyrolysis temperature from nanofibrillation is not due to damage of the crystalline cellulose by nano fibrillation, but the damage of the hemicellulose components in the surface of the cellulose microfibrils or the interface between the crystalline cellulose and hemicellulose. If the hemicellulose on the surface of crystalline cellulose could be removed from the NFC, then the decrease in the pyrolysis temperature could be suppressed.

Effects of programmed maintenance shutdowns on effluent quality of a bleached kraft pulp mill

Abstract Routinely, the mills perform programmed maintenance shutdowns (PMS) that can affect the characteristics of the effluents and the performance of the effluent treatment plant (ETP). A careful planning of the PMS, along with the use of industrial process sectorial spill control and the use of the emergency spill lagoon have considerably minimized these effects. The Suzano pulp mill located in Aracruz (Brazil) has three production lines and carry out, on average, PMS of each production line separately, every 15 months of operation. The purpose of the study was to evaluate the effects of the PMS on the effluent characteristics and performance of the ETP compared to the periods of normal operation. The results showed that during the PMS, the physicochemical characteristics of the raw and treated effluents were like those found during normal operation. The lower organic loads found in the effluents during the PMS periods were associated with the decrease of the flow rates and the increase of the hydraulic retention time of the ETP, causing a better performance of COD, BOD, TSS and AOX removal. A proper planning of the PMS improved the performance of the ETP and the treated effluent quality remained similar to those during the normal operating period.

The potential of different hemicelluloses extraction methods in conversion of environmentally friendly ECF and TCF bleached paper-grade bagasse soda pulp to dissolving-grade pulp

The potential of different hemicelluloses extraction methods in conversion of environmentally friendly ECF and TCF bleached paper-grade bagasse soda pulp to dissolving-grade pulp

Spray Drying Enzyme-Treated Cellulose Nanofibrils.

Enzyme-treated cellulose nanofibrils (CNFs) were produced via a lab-scale mass colloider using bleached kraft pulp (BKP) to evaluate their processability and power requirements during refining and spray-drying operations. To evaluate the energy efficiency in the CNF refining process, the net energy consumption, degree of polymerization (DP), and viscosity were determined. Less energy was consumed to attain a given fines level by using the endoglucanase enzymes. The DP and viscosity were also decreased using the enzymes. The morphological properties of the enzyme-pretreated spray-dried CNF powders (SDCNFs) were measured. Subsequently, the enzyme-pretreated SDCNFs were added to a PP matrix with MAPP as a coupling agent. The mixture was then compounded through a co-rotating twin-screw extruder to determine whether the enzyme treatment of the CNFs affects the mechanical properties of the composites. Compared to earlier studies on enhancing PMCs with SDCNF powders, this research investigates the use of enzyme-pretreated SDCNF powders. It was confirmed that the strength properties of PP increased by adding SDCNFs, and the strength properties were maintained after adding enzyme-pretreated SDCNFs.

Influence of temperature and pressure during thermoforming of softwood pulp

In this study, the influence of thermoforming conditions on the resulting material properties was investigated, which aimed at developing advanced wood-fiber-based materials for the replacement of fossil plastics. Two bleached softwood pulps were studied, i.e., northern bleached softwood Kraft pulp (NBSK) and chemi-thermomechanical softwood pulp (CTMP). The thermoforming conditions were varied between 2–100 MPa and 150–200 °C, while pressing sheets of 500 g/m² for 10 min to represent thin-walled packaging more closely. As our results showed, the temperature had a more pronounced effect on the CTMP substrates than on the Kraft pulp. This was explained by the greater abundance of lignin and hemicelluloses, while fibrillar dimensions and the fines content may play a role in addition. Moreover, the CTMP exhibited an optimum in terms of tensile strength at intermediate thermoforming pressure. This effect was attributed to two counteracting effects: 1) Improved fiber adhesion due to enhanced densification, and 2) embrittlement caused by the loss of extensibility. High temperatures likely softened the lignin, enabling fiber collapse and a tighter packing. For the Kraft substrates, the tensile strength increased linearly with density. Both pulps showed reduced wetting at elevated thermoforming temperature and pressure, which was attributed to hornification and densification effects. Here, the effect of temperature was again more pronounced for CTMP than for the Kraft fibers. It was concluded that the thermoforming temperature and pressure strongly affected the properties of the final material. The chemical composition of the pulps will distinctly affect their response to thermoforming, which could be useful for tailoring cellulose-based replacements for packaging products.

Flexibility of active center affects thermostability and activity of Penicillium canescens xylanase E

Xylanases are used in several industrial applications, such as feed additives, the bleaching of pulp and paper, and the production of bread, food, and drinks. Xylanases are required to remain active after heat treatment at 80–90 °C for 30 s to several minutes due to the conditions of feed pelleting. Also, xylanases need to be active at 60–70 °C for several hours while bleaching of pulp and paper or manufacturing of bread, food, and drinks is performed. Xylanases of the glycoside hydrolase family GH10 are good candidates for application in such processes because of their high thermostability and, in particular, as feed additives because of their insensitivity to protein inhibitors in cereal feeds. In the study, the thermostability of GH10 xylanase E from Penicillium canescens was improved to reach a half-inactivation period of 2 min at 80 °C compared to 21 s for the wild-type enzyme (WT). Enzymatic activity was increased by 22–48 % at 40–70 °C, which improved the action of the enzyme as a feed additive in the gastric system of animals and during bleaching of pulp and paper. Molecular dynamics simulations demonstrated lower flexibility of the tertiary structure of the engineered enzyme at elevated temperatures compared to WT. The residues W113, Q116, W313, and W321 in the (−1) and (−2) subsites for the substrate binding were less flexible. In the simulations, the engineered enzyme had a comparable content of α-helixes, 310-helixes, β-sheets, and β-bridges as WT, but a lower content of coils and a higher content of β-turns.

2,4,6-TCP migrates and transforms in different cultivated soil in China: Kinetic analysis and mechanistic modeling

Organochlorine pesticides are widely used in agriculture, wood preservation, pulp bleaching and other fields, which increased the pollution risk of cultivated land. In this study, a typical organochlorine pesticides-2,4,6-TCP was conducted as the target pollutants to investigated the migration and transformation characteristics in different cultivated soils in China. The results indicated that the adsorption of 2,4,6-TCP in soil samples was in order: black soil＞laterite＞fluvo-aquic soil, and the maximum adsorption was 71.0870, 27.0575 and 6.1292 mg/kg, respectively. The dispersion coefficient of black soil, laterite and fluvo-aquic soil was 0.0329, 0.0501 and 0.0149, and the hysteretic factor R was 5.381, 1.455 and 2.238, respectively, indicating that the migration ability of 2,4,6-TCP in different cultivated soils samples was in order: black soil＞laterite＞fluvo-aquic soil. The fitting results of one-dimensional migration model indicated that the model well reflected the migration and transformation of 2,4,6-TCP in different cultivated soil samples. Meanwhile, the Two-dimensional migration model fitting results indicated that the maximum concentration of 2,4,6-TCP of different cultivated soil samples were found along the longitudinal flow direction, reaching 40% of the initial pollution concentration at 15 m, corresponding to the center of the pollutant plume.

Evaluation of structure and compressive properties of eco-friendly cushioning materials based on starch and cellulose types

A reinforced eco-friendly cushioning material (ECM) comprising starch and cellulose material was developed. The ECM was prepared based on the starch type and cellulose material content; it was compared with commercial CMs. Different sizes of refined pulp (RP) and microfibrillated cellulose (MFC) were manufactured from hardwood bleached kraft pulp via beating and grinding, respectively. Thereafter, amylose-containing corn starch (CS) or amylopectin-only-containing glutinous rice starch (GS) was mixed with the manufactured cellulose materials. A slurry comprising starch and cellulose materials was homogenized for 2 min and lyophilized to prepare the ECM, after which the structure and strength characteristics of the prepared ECM were evaluated. The GS-prepared ECM produced a plate-like internal structure because of its amylopectin content, and amylose-containing CS exhibited a net-like shape. The cellulose materials offered support between starches with plate-like or net structure ECMs, and the pore shape was formed by adding MFC. As the cellulose material content increased, the strength of the ECM increased compared with that of the commercial CMs. Thus, ECMs with higher strength than their commercial counterparts could be manufactured with GS and cellulose materials.

EFFECTS OF BALL MILLING AND ENZYME TREATMENT ON CELLULOSE ACETYLATION

A novel process was developed to produce cellulose acetate from bleached hardwood kraft pulp (BHKP) through ball milling and cellulase treatment. The ball milling and/or cellulase treatment of BHKP increased the esterification reaction, but enzyme treatment reduced the viscosity of the produced cellulose acetate (CA). The degree of substitution (DS) values upon acetylation were 2.26 for BHKP, 2.61 for ball-milled BHKP and 2.91 for ball milled followed by cellulase treatment of BHKP. The prepared CA was also characterized by FTIR, XRD, TGA, 1H-NMR and SEM. A strong band for –OH stretching of cellulose disappeared and created a strong band for carbonyl (C=O) group on esterification of BHKP. The crystallinity index of BHKP was 63.3%, which completely disappeared on acetylation, demonstrating the successful esterification of cellulose. The initial weight loss of cellulose acetates was lower than that of the native cellulose, as observed in TGA, indicating the acetylated samples are less hydrophilic. 1H NMR spectroscopy confirmed the complete structure of cellulose acetate.

Nanocellulose Coating on Kraft Paper

Paper is a biodegradable material, but in food packaging, its hygroscopicity and porosity can cause food contamination due to the exchange of gasses and liquids with the environment. Therefore, it is important to use biodegradable materials for paper coatings, such as nanocellulose, which is chemically compatible with paper but less hygroscopic. The objective of this study was to evaluate the effectiveness of nanofibrillated cellulose (NFC) as a paper coating. NFC produced from bleached eucalyptus pulp was used as a coating on kraft paper sheets produced from Pinus pulp. To prepare the coating, two thicknesses of wet nanocellulose (1 mm and 2 mm) were tested, and two nanocellulose films made with the same thicknesses were evaluated. The morphological, physical, mechanical, and thermal properties of the composites were investigated. The presence of NFC improved the surface of the paper by filling the pores; consequently, the density and barrier properties were also improved. All mechanical properties were improved, with the highest increases observed for bursting and tensile strength; however, the films showed low bursting index values and null values for the tearing index. The thermal stability of the paper with NFC coatings met the minimum requirements for food packaging.