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The effect on softwood fiber wall nanostructure of kraft cooking, oxygen delignification and refining was evaluated by X-ray scattering. A recently developed simulation method for modelling small angle X-ray scattering (SAXS) data was used to estimate the apparent average sizes of solids (AAPS) and interstitial spaces in the fiber wall (AACS). Fiber saturation point and wide angle X-ray scattering were also used to calculate the pore volume in the fiber wall and the crystallite size of the fibril, respectively. The experimental modelled SAXS data was able to give consistent values for each kraft-cooked and oxygen-delignified pulp. Kraft delignification seems to have the major influence on the fiber nanostructure modification, while oxygen delignification has little or no significant impact even for different kappa numbers. The particle sizes values were more stable than the cavities sizes and no significant differences were seen between different delignification processes, refining or delignification degree. Pulps evaluated after PFI-refining, showed an increase in the fiber wall porosity evaluated by FSP and an increase in the interstitial spaces in the fiber wall, while the crystallite size and the particle sizes were very little or not affected at all., QC 20240703

From a circular economyperspective, one-pot strategies for theisolation of cellulose nanomaterials at a high yield and with multifunctionalproperties are attractive. Here, the effects of lignin content (bleachedvs unbleached softwood kraft pulp) and sulfuric acid concentrationon the properties of crystalline lignocellulose isolates and theirfilms are explored. Hydrolysis at 58 wt % sulfuric acid resulted inboth cellulose nanocrystals (CNCs) and microcrystalline celluloseat a relatively high yield (>55%), whereas hydrolysis at 64 wt% gaveCNCs at a lower yield (<20%). CNCs from 58 wt % hydrolysis weremore polydisperse and had a higher average aspect ratio (1.5-2x),a lower surface charge (2x), and a higher shear viscosity (100-1000x).Hydrolysis of unbleached pulp additionally yielded spherical nanoparticles(NPs) that were <50 nm in diameter and identified as lignin bynanoscale Fourier transform infrared spectroscopy and IR imaging.Chiral nematic self-organization was observed in films from CNCs isolatedat 64 wt % but not from the more heterogeneous CNC qualities producedat 58 wt %. All films degraded to some extent under simulated sunlighttrials, but these effects were less pronounced in lignin-NP-containingfilms, suggesting a protective feature, but the hemicellulose contentand CNC crystallinity may be implicated as well. Finally, heterogeneousCNC compositions obtained at a high yield and with improved resourceefficiency are suggested for specific nanocellulose uses, for instance,as thickeners or reinforcing fillers, representing a step toward thedevelopment of application-tailored CNC grades., QC 20231122

In recent years, there has been extensive research into the development of cheaper and more sustainable carbon fiber (CF) precursors, and air-gap-spun cellulose-lignin precursors have gained considerable attention where ionic liquids have been used for the co-dissolution of cellulose and lignin. However, ionic liquids are expensive and difficult to recycle. In the present work, an aqueous solvent system, cold alkali, was used to prepare cellulose-lignin CF precursors by wet spinning solutions containing co-dissolved dissolving-grade kraft pulp and softwood kraft lignin. Precursors containing up to 30 wt% lignin were successfully spun using two different coagulation bath compositions, where one of them introduced a flame retardant into the precursor to increase the CF conversion yield. The precursors were converted to CFs via batchwise and continuous conversion. The precursor and conversion conditions had a significant effect on the conversion yield (12-44 wt%), the Young's modulus (33-77 GPa), and the tensile strength (0.48-1.17 GPa), while the precursor morphology was preserved. Structural characterization of the precursors and CFs showed that a more oriented and crystalline precursor gave a more ordered CF structure with higher tensile properties. The continuous conversion trials highlighted the importance of tension control to increase the mechanical properties of the CFs., QC 20230125

High alkali impregnation (HAI) increases the total yield of softwood pulps following kraft cooking. This yield improvement is also maintained after oxygen delignification. This study evaluates how bleaching with either chlorine dioxide or hydrogen peroxide affects the final yield of samples obtained with standard and HAI. The chemical composition, viscosity, brightness, mechanical and morphological properties were studied. Compared to cooking after standard impregnation the yield improvement achieved by HAI was preserved in both types of bleaching sequences (2% units for chlorine dioxide and 4% units for hydrogen peroxide). The introduction of charged groups into the cellulose fibers was higher with hydrogen peroxide bleaching than with chlorine dioxide however, no significant impact was seen on the swelling or mechanical properties. The brightness was higher for the pulps bleached with chlorine dioxide compared with hydrogen peroxide. Hydrogen peroxide bleaching resulted in similar brightness development for both standard and HAI. Fibers bleached with chlorine dioxide had the highest curl index (16-17%) compared to the fibers bleached with hydrogen peroxide (15%)., QC 20221114

This study investigated whether the yield improvement after high alkali impregnation (HAI) is maintained after oxygen delignification and whether the potential of oxygen delignification to increase the mechanical properties is affected by high alkali impregnation. The yield improvement achieved by high alkali impregnation (1 %) was preserved after oxygen delignification, particularly of glucomannan. The total fiber charge and swelling increased after oxygen delignification regardless of the type of impregnation in the cooking step. The tensile index improvement obtained by oxygen delignification was retained if this was preceded by high alkali impregnation. The stiffness index was higher and elongation slightly lower after HAI impregnation than after a standard (REF) impregnation. Fibers obtained through high alkali impregnation seem to be slightly less deformed and slightly wider than fibers obtained after a standard impregnation., QC 20221114

The fiber properties after oxygen delignification and kraft pulping were studied by looking into the chemical characteristics and morphology. The effect of the two processes on the fibers was evaluated and compared over a wider kappa number range (from 62 down to15). Wide-angle X-ray scattering, nuclear magnetic resonance and fiber saturation point were used to characterize the fiber network structure. Fiber morphology and fiber dislocations were evaluated by an optical image analysis. The total and surface fiber charges were studied by conductometric and polyelectrolyte titrations. The fiber wall supramolecular structure, such as crystallinity, size of fibril aggregates, pore size and pore volume, were similar for the two processes. The selectivity, in terms of carbohydrate yield, was equal for kraft cooking and oxygen delignification, but the selectivity in terms of viscosity loss per amount of delignification is poorer for oxygen delignification. Clearly more fiber deformations (2–6% units in curl index) in the fibers after oxygen delignification were seen. Introduction of curl depended on the physical state of the fibers, i.e. liberated or in wood matrix. In the pulping stage, the fiber continue to be supported by neighboring fibers, as the delignified chips maintain their form. However, in the subsequent oxygen stage the fibers enter in the form of pulp (liberated fibers), which makes them more susceptible to changes in fiber form., QC 20220301

Charged groups in pulp have been shown to enhance the tensile strength of the paper produced from the pulp. Oxygen delignification introduces charged groups and it is of interest to determine how the delignification should be distributed between the cooking and the oxygen stage with respect to mechanical properties. A number of unbleached kraft cooked and oxygen delignified pulps within a wide kappa number range were produced and refined, and the effects of the refining on the morphology and mechanical properties were studied. The WRV correlated with the fiber charge and at a given fiber charge, kraft cooked and oxygen delignified pulps had the same WRV development in refining, although they had significantly different kappa numbers. The tensile strength development during refining depends on the fiber rigidity which is affected by the lignin content, the fiber charge and the chemical and mechanical processes used. Refining increased the curl of the kraft cooked pulps and decreased the curl of oxygen delignified pulps, irrespective of kappa number. A greater increase in tensile strength was seen for the pulps with a higher fiber charge and WRV, probably because of the greater degree of fibrillation achieved in the beating process. Despite the greater fiber deformation in the oxygen delignified pulps, the strength can be increased by a larger amount of charged groups and a greater swelling of the fibers., QC 20211210

Impregnation with high initial concentration is fast and efficient, leading to a homogeneous delignification in the subsequent cook, resulting in improved screened pulp yield. To obtain high initial alkali concentration, the white liquor flow needs to be significantly increased. The moisture content of the wood chips and the alkali concentration of the white liquor limit the initial alkali concentration of the impregnation liquor that can be reached. It is therefore of interest to evaluate the possibility to implement high alkali impregnation (HAI) industrially and the consequences this would have on the mill system. The effect of HAI on mass and energy balances in a kraft pulp mill has been studied using mill model simulations. The sensitivity to disturbances in important parameters for process control has been compared to impregnation scenarios used industrially. It was shown that high initial alkali concentration can be achieved on industrial scale by increased white liquor flow. HAI has a positive effect on recovery flows and reduces the need for make-up chemicals. The HAI concept is less sensitive to variations in process parameters, such as chip moisture and white liquor concentration, thus diminishing the risk of alkali depletion in chip cores. © 2019 Brännvall and Kulander.

A rapeseed straw biorefinery process was demonstrated with more than 50% of the straw recovered as products. Xylan with a weight-average molecular weight of 56 760 g/mol was extracted in an alkaline step. The straw residue was subjected to soda pulping, resulting in cellulose-rich fibers and a lignin-rich liquid fraction. The lignin contained syringyl and guaiacyl aromatic structural units in a 1/0.75 ratio. The cellulose pulp was bleached, resulting in a cellulose fraction of 85% purity and a crystallinity index (CI) of 83%. Two grades of nanocellulose, CNF and CNC, were isolated from the bleached pulp. The CNF was very heterogeneous in size with an average diameter of 4 nm and an average length of 1177 nm. The CNC had an average diameter of 6 nm and an average particle length of 193 nm. CNF and CNC had good thermal stability and an aspect ratio of 294 and 32, respectively.

Pulp yield can be improved by a more homogeneous delignification of the chips, achieved by improved impregnation prior to the cooking stage. Complete and efficient impregnation is obtained by increasing the diffusion rate by means of an impregnation liquor with a high initial effective alkali concentration (HIEAC). In the present study, the effect of HIEAC in the impregnation was evaluated and compared to a reference impregnation procedure and a prolonged impregnation. After the various impregnation scenarios, the alkali concentration was always adjusted to the same level in the beginning of the cooking stage. Impregnation with a HIEAC resulted in yield improvements by 1-1.5% units, due to a higher cellulose yield and possibly also to higher yield of glucomannan. The HIEAC with an even alkali distribution within the chips prior to the cooking stage resulted in a more uniform delignification carbohydrate degradation. Yield increase obtained by uniform delignification is due to both decreased shives content as well as less secondary peeling.

Xylan extracted from rapeseed straw was chemically modified to gain hydrophobic and thermoplastic properties via macroinitiator formation followed by a free radical grafting-from polymerization with octadecyl acrylate. Biocomposites were then prepared by incorporation of 5 or 20% (w/w) rapeseed straw xylan into a poly(ε-caprolactone) (PCL) matrix by melt extrusion. The grafted xylan was homogeneously distributed within the biocomposite and reinforced the PCL matrix while at the same time preserving the ability to elongate to tensile strains >500%. Analogous biocomposites made from unmodified xylan in a PCL matrix resulted in heterogeneous mixtures and brittle tensile properties.

The authors regret that the original version of this article unfortunately contained a mistake in Table 5. The correct Table 5 and associated text is given below. “The rapeseed hemicellulose films presented here had strain-at-break values of 70% (C) and 90% (H), even with no added plasticizers (Table 5).” The authors would like to apologise for any inconvenience caused.

Rapeseed straw consists of a hard epidermis that is rich in hemicellulose and lignin and a sponge-like interior that consists mainly of cellulose. The stems were subjected to water, alkali or acid as extraction medium. The effects of the extraction conditions were quantified using severity factors and by comparing the effects of different extraction pHs, temperatures and times. Extraction with alkali resulted in a higher yield, 47 g/100 g straw in, compared to water, 6 g/100 g straw in, or an acidic, 5 g/100 g straw in, extraction process. An increase in temperature improved the extraction yield; in particular, more xylan was extracted at an elevated temperature and higher alkalinity. However, at high alkalinity, increased extraction temperatures led to a reduction in the recovery of glucomannan. The highest molecular weights (similar to 35,000 g/mol) of the extracted hemicelluloses were obtained using extraction procedures with 1.5 M NaOH at 110 degrees C and autohydrolysis at 150 degrees C. While these two parameter settings had very similar severity factors, extraction under basic conditions afforded an extract rich in xylan and low in lignin content, whereas autohydrolysis generated a glucomannan-rich extract., QC 20170202

The effect on kraft cooking proceeded by an impregnation stage performed at 130 degrees C for 30 min was compared to kraft cooking following prolonged impregnation at 105 degrees C for 60-120 min. The alkali consumed during impregnation varied depending on the temperature and time of the impregnation stage. In order to study the impact of the impregnation stage on the subsequent kraft cook, the initial concentration of effective alkali was adjusted to be initially the same in all cooks before cooking for 180-290 min. The alkali consumed in the impregnation stage affected the alkali profile of the cooking stage. The more alkali consumed in impregnation, the lower the demand in cooking. Higher alkali consumption in the impregnation stage also led to faster delignification in the cooking stage. Prolonged impregnation resulted in 1-1.5 percentage points higher yield compared to the reference case. The yield increment was due to a higher cellulose retention. Although the impregnation time was prolonged from 30 min up to 2 h, the higher delignification rate and higher yield only decreased the production rate with 11% compared to the reference., QC 20170505

QC 20190220

Presteaming is a well-established technique in pulp mills, which improves cooking liquor impregnation by removing air from within and between chips. The aim of the study was to investigate how conditions during steaming affect the subsequent kraft cook and properties of the obtained pulp. It was found that higher pressure and temperature during chip presteaming led to increased degradation and dissolution of hemicelluloses. Lower refinability and tensile index was obtained for pulps cooked after presteaming at high pressure and for a long time., QC 20160530

The potential of seven kraft cook materials to become functional char materials and fuels is investigated. Thermogravimetric analysis was used to study the thermal properties while a model-free isoconversional method was used to derive kinetic rate expressions. Black liquor precipitates had lower thermal stability (20-60 K lower) than pulps and spruce wood and the precipitates decomposed in a wider temperature range, producing chars with similar or higher thermal stability than char from pulps, but lower than those from spruce wood. Samples suitable to produce char were identified based on char yield, devolatilization rate and charring temperature. The highest char yield (46%), achieved from a precipitate, was more than twice as high as that from spruce powder. Under the studied conditions none of the materials had a pyrolysis process that for the whole conversion range could be described with a single set of kinetic parameters. The apparent activation energy varied between 170-260 kJ/mol for the pulps and 50-650 kJ/mol for the precipitates. The derived kinetic parameters were validated by predicting the conversion at a heating rate outside the range used for its derivation and at quasi isothermal conditions. Both these tests gave satisfactory results in good agreement with experimental data., QC 20160721

The composition, molecular weight (MW), and chemical structure of technical lignins as byproducts of pulping influence their application in terms of physical and chemical properties, reactivity, and performance. It is important to know how the analytical data of technical lignins are influenced by the wood species and the parameters of pulping. The present study focuses on kraft pulping and how the wood species (eucalyptus, pine, and spruce) and variable cooking times influence the characteristics of dissolved lignins. The black liquor (BL) was recovered after three different cooking times and the precipitated lignin was characterized by total acid hydrolysis including the determination of the acid insoluble part (Klason lignin, KL) and the sugars in the hydrolysate, elemental analysis, 31P NMR spectroscopy, analytical pyrolysis (Py-GC/MS), gel permeation chromatography (GPC), thermogravimetry (TG), and differential scanning calorimetry (DSC). The results indicate that the phenolic OH content, MW and glass transition temperature increased with longer cooking times for the softwood (SW) lignins. These lignins had also a higher MW (M-w 5500-8000 g mol(-1)), than the eucalyptus lignin (M-w 2200-2400 g mol(-1)). Eucalyptus lignin had higher sulfur content compared to SW., QC 20170118