Andrea Borgards

Dissolution Behavior of Different Celluloses

Celluloses from different origins were dissolved stepwise in N,N-dimethylacetamide/lithium chloride (9% v/w; DMAc/LiCl) with the aim to study the time course of the dissolution process, completeness of dissolution in the dissolved fractions, possible discrimination effects, and differences between the celluloses. Cellulosic pulps from both annual plants and different wood species were analyzed. The obtained fractions were subject to gel permeation chromatography (GPC) with multiple detection to monitor the development of molecular mass distribution (MMD), molecular mass, and recovered mass. The dissolution behavior of accompanying xylans was followed by quantitative analysis of the uronic acids by fluorescence labeling--GPC. The morphological changes at the remaining fibers in the stepwise dissolution were addressed by SEM. The time needed to dissolve completely the cellulosic pulp differed from species to species, mainly between pulps from annual plants and pulps from wood. Annual plants generally needed much longer to dissolve completely. In the beginning of the dissolution, the dissolved fractions of annual plants showed a distinct discrimination effect because they were enriched in hemicellulose. By contrast, wood pulps dissolve fast and without distinct changes in the MMD of the dissolved fractions over time. Bagasse pulp is an exception to the observation for annual plants and rather resembled the behavior of wood celluloses. Prolonged dissolution times, as often practiced in cellulose GPC, do not lead to any improvements regarding the determination of molecular mass, MMD, and recovered mass of injected sample, so that the dissolution times required for reliable GPC analysis can be significantly shortened, which will be important for biorefinery analytics with high numbers of samples.

Determination of carbohydrate- and lignin-derived components in complex effluents from cellulose processing by capillary electrophoresis with electrospray ionization-mass spectrometric detection

Degradation products from lignocellulosic materials receive increasing attention due to the continuously growing interest in their utilization. The inherent structural variance of lignocellulosics combined with the intricacy of lignocellulosic processing (e.g. pulping of wood and bleaching of cellulosic pulps) and the complexity of degradation processes occurring therein result in rather complex mixtures in the process streams and effluents that contain a large quantity of structurally different degradation products. This is true for most processing steps, but also for degradation reactions occurring during aging of lignocellulosic materials, such as paper, cellulosic tissue or textiles. In order to render such mixtures better analytically accessible than hitherto possible a CE-ESI-MS method was established for the simultaneous determination of aliphatic carboxylic acids from the degradation of (hemi)celluloses and aromatic compounds from lignin degradation. CE and ESI-MS parameters have been optimized towards sensitivity and good reproducibility. The method was tested in two real-world scenarios: the determination of major components in effluents from bleaching stages in the pulp and paper industry, and the analysis of degradation products in extracts of naturally aged papers. The advantages and drawbacks of this approach are critically discussed.

Degradation products of lignocellulosics in pulp mill effluents - comparison and evaluation of different gas chromatographic techniques for a comprehensive analysis.

Abstract Pulp mill effluents contain potentially valuable compounds and will gain even greater importance than today in future biorefinery scenarios as possible resources. Analysis of effluents of process streams is not straightforward because of the vast variety of substances embedded in the complex inorganic matrix of high concentration. In the present comparative investigation, different combinations of gas chromatography (GC) and derivatisation techniques were tested and critically evaluated aiming at a comprehensive description of all major compound classes (low-molecular weight and long-chain carboxylic acids, lignin fragments, carbohydrates and aldehydes). As derivatisation techniques, trimethylsilylation, (trimethylsilyl)methylation and methylation were applied. In addition, the effluents were analysed by pyrolysis-GC/mass spectrometry (MS), either directly or with simultaneous methylation. The study provides comprehensive information on the composition of effluents, the suitability of the various combinations of derivatisation and GC/MS techniques. The discrimination effects of the different approaches are compared. The comprehensive analytical approach led to a coherent balance in terms of the contribution of the major portion of organic compounds to the total organic carbon (TOC) content in pulp mill effluents.