Abstract

AbstractSeparation of the heterogeneous lignin macromolecule in fractions with increased homogeneity, as well as different structural (molar mass) and functional (hydroxy groups, ‐OH) features is important in terms of its use as a chemical building block. For this purpose, three thermal separation techniques were investigated and compared: solvent extraction, successive precipitation and ultrafiltration. One important issue in this context is the utilization of organic solvents with low boiling points to ensure a simple and efficient recovery. In addition to a softwood Kraft lignin (Indulin AT) as reference lignin, two sulfur‐free Organosolv lignins from short rotation coppice (“poplar with bark”) and from the energy grass Miscanthus × gigantheus were investigated. The lignins were separated into low, medium and high molecular weight fractions. Due to the different initial structural features and the associated varying solubility properties in such lignins, different organic solvents were needed for dissolution and precipitation of the individual lignin fractions. The polarity of the used solvent is one key factor regarding the yield of the soluble fraction and the success of molecular sorting into low, medium, and high molecular weight. Further structural features, for example the aliphatic OH‐group content increased with rising molecular weight of poplar, miscanthus, and Kraft lignin from minimum 0.72, 0.3, and 1.6 mmol/g to maximum 2.4, 1.6, and 2.8 mmol/g, respectively. The number of phenolic OH‐groups decreased from maximum 3.8, 4.3, and 4.2 to minimum 1.4, 2.7, and 2.9, respectively. The presented work illustrate options regarding the molecular sorting of several lignin types with three thermal techniques into fractions differing in key properties (yield, molecular weight, polydispersity, functional groups) for material applications.

Highlights

  • As the demand for fossil oil has increased in recent decades and tends to continue this way, the demand for alternative and renewable resources has increased with regard to substitute limited fossil resources (International Energy Agency, 2013; Laurichesse & Avérous, 2014)

  • For example the aliphatic OH‐group content increased with rising molecular weight of poplar, miscanthus, and Kraft lignin from minimum 0.72, 0.3, and 1.6 mmol/g to maximum 2.4, 1.6, and 2.8 mmol/g, respectively

  • The three investigated lignins were successfully fractionated into low (LMW), medium (MWW) and high molecular weight (HMW) fractions by solvent extraction, successive precipitation and membrane filtration

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Summary

Introduction

As the demand for fossil oil has increased in recent decades and tends to continue this way, the demand for alternative and renewable resources has increased with regard to substitute limited fossil resources (International Energy Agency, 2013; Laurichesse & Avérous, 2014). | 207 sustainable substitution for this fossil resources in chemical applications might be lignin due to its phenolic basic structure as bio‐based building block for value‐added products like epoxy resins or polyurethane foams (Asada, Basnet, Otsuka, Sasaki, & Nakamura, 2015; Wysocka, Szymona, McDonald, & Mamiński, 2016). Lignin is a three‐dimensional polymer and as part of the lignocellulosic biomass the second most abundant natural polymer next to cellulose. The lignin structure consists of three phenolic monomer building blocks p‐hydroxyphenyl (H), guaiacyl (G), and syringyl (S) which are linked irregular through ether and carbon‐carbon bonds resulting in heterogenic and hydrophobic macromolecules (Dorrestijn, Laarhoven, Arends, & Mulder, 2000; Sjöström, 1993). The structure of lignin as well as the amount of the three monomer units depends on the origin and type of the lignocellulosic biomass. Softwood lignin is almost exclusively built of G units, hardwood contains S and G units while grass lignin consists of an almost equal H/G/S mixture (Gellerstedt & Henriksson, 2008)

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