RESUMO
A new chemical modification protocol to generate N-lignins is presented, based on Indulin AT and Mg2+-lignosulfonate. The already known ammonoxidation reaction in liquid phase was used as a starting point and stepwise optimised towards a full solid-state approach. The "classical" liquid ammonoxidation products, the transition products from the optimization trials, as well as the "solid-state" products were comprehensively analysed and compared to the literature. The N-lignins obtained with the conventional ammonoxidation protocol showed the same properties as reported. Their molar mass distributions and the hydroxy group contents, hitherto not accessible due to solubility problems, were measured according to a recently reported protocol. N-Indulin showed an N-content up to 11 wt% and N-lignosulfonate up to 16 wt%. The transition experiments from liquid to solid-state gave insights into the influence of chemical components and reaction conditions. The use of a single chemical, the urea-hydrogen peroxide complex (UHP, "carbamide peroxide"), was sufficient to generate N-lignins with satisfying N-content. This chemical acts both as an N-source and as the oxidant. Following the optimization, a series of solid-state ammonoxidation tests were carried out. High N-contents of 10% in the case of Indulin and 11% in the case of lignosulfonate were obtained. By varying the ratio of UHP to lignin, the N-content can be controlled. Structural analysis showed that the N is organically bound to the lignin, similar to the "classical" ammonoxidation products obtained under homogeneous conditions. Overall, a new ammonoxidation protocol was developed which does not require an external gas supply nor liquids or dissolved reactants. This opens the possibility for carrying out the lignin modification in closed continuous reactor systems, such as extruders. The new, facile solid-state protocol will hopefully help N-lignins to find more consideration as a fertilizing material and in soil-improving materials.
RESUMO
31P nuclear magnetic resonance (NMR) spectroscopy is the most common and most accurate analytical method to quantitatively determine the hydroxy group contents of technical lignins. However, for lignosulfonates, liquid-state NMR analysis is often limited due to solubility problems in commonly used solvent systems, which may arise from the broad range of lignosulfonates from different wood sources, pulping conditions, and purification procedures used in biorefineries. Finding a suitable solvent system is even more difficult for chemically modified or fractionated lignosulfonates. In this study, a novel and fast approach for the solubilization of genuine, modified, and fractionated lignosulfonates and subsequent quantitative analysis of hydroxy groups by 31P NMR after derivatization with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane is presented. The implementation of the ionic liquid 1-ethyl-3-methylimidazolium chloride [emim]Cl to the already validated and commonly used DMF/pyridine solvent system caused complete solubility of previously insoluble samples, especially in the case of hard-to-dissolve ammonoxidized lignosulfonates. The applicability, accuracy, and robustness of the novel solvent system for 31P NMR analysis were comprehensively investigated with lignin model compounds and commercial lignosulfonates, including otherwise insoluble, real-world lignosulfonate specimens. The results were compared to the conventional DMF/pyridine solvent system. With the novel solvent system in hand, a much larger number of different lignosulfonates can be analyzed. In particular, the hydroxy group contents of ammonoxidized lignosulfonates were determined for the first time directly by 31P liquid-state NMR.
Assuntos
Lignina , Madeira , Lignina/análogos & derivados , Lignina/química , Espectroscopia de Ressonância Magnética , SolventesRESUMO
The reuse of steeping lye is crucial for the sustainable production of viscose fibers. Steeping lye contains hemicellulose and many alkaline degradation products, such as organic acids, so that its purification can be evaluated in terms of total organic carbon removal. When considering purification by membrane filtration, intermolecular interactions between hemicellulose and organic acids can strongly affect their retention efficiency. Herein, we give more insights into the ultrafiltration and nanofiltration of steeping lye and corresponding model solutions. Furthermore, we studied the impact of total organic carbon concentration, hemicellulose concentration and sodium hydroxide concentration on the membrane performance. Hydrogen bonds between hemicellulose and certain types of hydroxy acids increased the retention of the latter. In contrast, charge based repulsion forces led to a decreased retention of a certain type of hydroxy acids. It can be clearly shown that taking intermolecular interactions into account is highly important for the description of complex multicomponent mixtures. In addition, the results can be extended to other, highly alkaline process streams with organic content, such as Kraft pulping liquors.
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Fully dissolved cellulose samples are a requirement for reliable size exclusion chromatography (SEC). Although most of the standard dissolving pulps can be completely dissolved in the N,N-dimethylacetamide/lithium chloride (DMAc/LiCl) solvent system, some cellulose samples (e.g., regenerated cellulose fibers) have poor solubility and therefore have a limited access to molar mass measurements. For improving the latter, different activation steps have been developed. In order to obtain complete solutions for subsequent SEC analysis, the scope of this study was to further improve established methods by elucidating the major influential factors of sample preparation. In addition, the degree of stretching in artificial fibers was examined for viscose fibers. Therefore, activation steps in DMAc or dimethyl sulfoxide (DMSO) and subsequent dissolution in DMAc/LiCl were analyzed with swelling and dissolution kinetics. The time needed for maximum swelling was found to be the optimum activation time. Turbidity measurement was introduced to observe dissolution kinetics as an indicator of dissolution quality. Thus, the duration, as well as the number of steps toward dissolution, was optimized to enhance the throughput in the overall analysis of a large variety of hitherto poorly soluble cellulose samples. A comparison of the MMDs of completely soluble reference materials obtained with the intensified conventional method, and the developed method demonstrated that the latter has no adverse influence on the results.
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Celulose/química , Acetamidas/química , Cloreto de Lítio/química , Peso Molecular , Solubilidade , SolventesRESUMO
The high-yield separation of polymeric parts from wood-derived lignocellulosic material is indispensable in biorefinery concepts. For the separation of cellulose and xylan from hardwood paper pulps to obtain pulps of high cellulose contents, simple alkaline extractions were found to be the most suitable technology, although having certain limitations. These are embodied by residual alkali resistant xylan incorporated in the pulp matrix. Further purification in order to produce pure cellulose with a low uniformity could be achieved selectively degrading residual xylan and depolymerizing the cellulose macromolecules by xylanase and cellulase. The latter help to adjust cellulose chain lengths for certain dissolving pulp grades while reducing the demand for ozone in subsequent TCF bleaching. Experiments applying different commercially available enzyme preparations revealed the dependency of xylanase performance on the residual xylan content in pulps being stimulated by additional cellulase usage. The action of the latter strongly depends on the cellulose allomorphy confirming the impact of the pulp morphology. Hence, the combined application of both types of enzymes offers a high potential for upgrading pulps in order to produce a pure and high-value cellulose product.
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Celulose/isolamento & purificação , Papel , Álcalis , Biotecnologia , Celulase/metabolismo , Celulose/metabolismo , Endo-1,4-beta-Xilanases/metabolismo , Madeira/químicaRESUMO
Nuclear magnetic resonance, mid and near infrared, and ultra violet (UV) spectra of wood contain information on its chemistry and composition. When solid wood samples are analysed, information on the molecular structure of the lignocellulose complex of wood e.g. crystallinity of polysaccharides and the orientation of the polymers in wood cell walls can also be gained. UV and infrared spectroscopy allow also for spatially resolved spectroscopy, and state-of-the-art mapping and imaging systems have been able to provide local information on wood chemistry and structure at the level of wood cells (with IR) or cell wall layers (with UV). During the last decades, these methods have also proven useful to follow alterations of the composition, chemistry and physics of the substrate wood after fungi had grown on it as well as changes of the interactions between the wood polymers within the lignocellulose complex caused by decay fungi. This review provides an overview on how molecular spectroscopic methods could contribute to understand these degradation processes and were able to characterise and localise fungal wood decay in its various stages starting from the incipient and early ones even if the major share of research focussed on advanced decay. Practical issues such as requirements in terms of sample preparation and sample form and present examples of optimised data analysis will also be addressed to be able to detect and characterise the generally highly variable microbial degradation processes within their highly variable substrate wood.
Assuntos
Fungos/metabolismo , Compostos Orgânicos/análise , Análise Espectral/métodos , Madeira/química , Madeira/metabolismoRESUMO
Spruce wood that had been degraded by brown-rot fungi (Gloeophyllum trabeum or Poria placenta) exhibiting mass losses up to 16% was investigated by transmission Fourier transform infrared (FT-IR) imaging microscopy. Here the first work on the application of FT-IR imaging microscopy and multivariate image analysis of fungal degraded wood is presented and the first report on the spatial distribution of polysaccharide degradation during incipient brown-rot of wood. Brown-rot starts to become significant in the outer cell wall regions (middle lamellae, primary cell walls, and the outer layer of the secondary cell wall S1). This pattern was detected even in a sample with non-detectable mass loss. Most significant during incipient decay was the cleavage of glycosidic bonds, i.e. depolymerisation of wood polysaccharides and the degradation of pectic substances. Accordingly, intramolecular hydrogen bonding within cellulose was reduced, while the presence of phenolic groups increased.
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Beech wood (Fagus sylvatica L.) veneers were cultivated with white and brown rot fungi for up to 10 weeks. Fungal wood modification was traced with Fourier transform near infrared (FT-NIR) and Fourier transform mid infrared (FT-MIR) methods. Partial least square regression (PLSR) models to predict the total lignin content before and after fungal decay in the range between 17.0% and 26.6% were developed for FT-MIR transmission spectra as well as for FT-NIR reflectance spectra. Weight loss of the decayed samples between 0% and 38.2% could be estimated from the wood surface using individual PLSR models for white rot and brown rot fungi, and from a model including samples subjected to both degradation types.