Production and Properties of Lignin Nanoparticles from Ethanol Organosolv Liquors-Influence of Origin and Pretreatment Conditions

Despite major efforts in recent years, lignin as an abundant biopolymer is still underutilized in material applications. The production of lignin nanoparticles with improved properties through a high specific surface area enables easier applicability and higher value applications. Current precipitation processes often show poor yields, as a portion of the lignin stays in solution. In the present work, lignin was extracted from wheat straw, spruce, and beech using ethanol organosolv pretreatment at temperatures from 160–220 °C. The resulting extracts were standardized to the lowest lignin content and precipitated by solvent-shifting to produce lignin micro- and nanoparticles with mean hydrodynamic diameters from 67.8 to 1156.4 nm. Extracts, particles and supernatant were analyzed on molecular weight, revealing that large lignin molecules are precipitated while small lignin molecules stay in solution. The particles were purified by dialysis and characterized on their color and antioxidant activity, reaching ASC equivalents between 19.1 and 50.4 mg/mg. This work gives detailed insight into the precipitation process with respect to different raw materials and pretreatment severities, enabling better understanding and optimization of lignin nanoparticle precipitation

Lignin from Micro- to Nanosize: Production Methods

Lignin is the second most abundant biopolymer after cellulose. It has long been obtained as a by-product of cellulose production in pulp and paper production, but had rather low added-value applications. A changing paper market and the emergence of biorefinery projects should generate vast amounts of lignin with the potential of value addition. Nanomaterials offer unique properties and the preparation of lignin nanoparticles and other nanostructures has therefore gained interest as a promising technique to obtain value-added lignin products. Due to lignin’s high structural and chemical heterogeneity, methods must be adapted to these different types. This review focuses on the ability of different formation methods to cope with the huge variety of lignin types and points out which particle characteristics can be achieved by which method. The current research’s main focus is on pH and solvent-shifting methods where the latter can yield solid and hollow particles. Solvent shifting also showed the capability to cope with different lignin types and solvents and antisolvents, respectively. However, process conditions have to be adapted to every type of lignin and reduction of solvent demand or the integration in a biorefinery process chain must be focused

Production and Characterisation of Pickering Emulsions Stabilised by Colloidal Lignin Particles Produced from Various Bulk Lignins

The use of lignin, an abundant phenolic bio-polymer, allows us to transform our fossil-based economy into a sustainable and bio-based economy. The transformation of bulk lignin into colloidal lignin particles (CLPs) with well-defined surface chemistry and morphology is a possible way to cope with the heterogeneity of lignin and use it for material applications. These CLPs can be used as emulsifiers in so-called Pickering emulsions, where solid particles stabilise the emulsion instead of environmentally harmful synthetic surfactants. This work investigates the application of CLPs produced from various bulk lignins as a stabiliser in o/w Pickering emulsions with two different oil phases (solid and liquid state). The CLPs had a primary particle size of 28 to 55 nm. They were successful in stabilising oil-in-water Pickering emulsions with high resistance to coalescence and a strong gel-like network. This enables novel applications for CLPs in the chemical and cosmetic industries, and can replace fossil-based and synthetic ingredients

Lignin from Micro- to Nanosize: Applications

Micro- and nanosize lignin has recently gained interest due to improved properties compared to standard lignin available today. As the second most abundant biopolymer after cellulose, lignin is readily available but used for rather low-value applications. This review focuses on the application of micro- and nanostructured lignin in final products or processes that all show potential for high added value. The fields of application are ranging from improvement of mechanical properties of polymer nanocomposites, bactericidal and antioxidant properties and impregnations to hollow lignin drug carriers for hydrophobic and hydrophilic substances. Also, a carbonization of lignin nanostructures can lead to high-value applications such as use in supercapacitors for energy storage. The properties of the final product depend on the surface properties of the nanomaterial and, therefore, on factors like the lignin source, extraction method, and production/precipitation methods, as discussed in this review

Lignin from Micro- to Nanosize: Production Methods

Lignin is the second most abundant biopolymer after cellulose. It has long been obtained as a by-product of cellulose production in pulp and paper production, but had rather low added-value applications. A changing paper market and the emergence of biorefinery projects should generate vast amounts of lignin with the potential of value addition. Nanomaterials offer unique properties and the preparation of lignin nanoparticles and other nanostructures has therefore gained interest as a promising technique to obtain value-added lignin products. Due to lignin’s high structural and chemical heterogeneity, methods must be adapted to these different types. This review focuses on the ability of different formation methods to cope with the huge variety of lignin types and points out which particle characteristics can be achieved by which method. The current research’s main focus is on pH and solvent-shifting methods where the latter can yield solid and hollow particles. Solvent shifting also showed the capability to cope with different lignin types and solvents and antisolvents, respectively. However, process conditions have to be adapted to every type of lignin and reduction of solvent demand or the integration in a biorefinery process chain must be focused

High Temperature Lignin Separation for Improved Yields in Ethanol Organosolv Pre-Treatment

The full utilization of renewable raw materials is necessary for a sustainable economy. Lignin is an abundant biopolymer, but is currently mainly used for energy production. Ethanol organosolv pre-treatment produces high-quality lignin, but still faces substantial economic challenges. Lignin solubility increases with temperature, and previous studies have shown that it reprecipitates during cooling after the pre-treatment. Thus, a possibility for the optimization of lignin production with this process can be the separation of extract and residual biomass at high temperatures. In this work, lignin was extracted from wheat straw at 180 °C, and the extract was separated from the remaining solids at several temperatures after the pre-treatment. The results show that 10.1 g/kg of lignin and 2.2 g/kg of carbohydrates are dissolved at the pre-treatment temperature of 180 °C, which is reduced to 8.6 g/kg of lignin and 1.2 g/kg of carbohydrates after cooling. The precipitation of lignin separated from the extracts at 180 °C showed that a higher lignin concentration at high temperatures results in a 46% improvement in the yield of solid lignin, while there was no significant impact on the lignin purity

UV-Vis Spectroscopy and Chemometrics for the Monitoring of Organosolv Pretreatments

Lignocellulosic agricultural side products like wheat straw are widely seen as an important contribution to a sustainable future economy. However, the optimization of biorefinery processes, especially the pretreatment step, is crucial for an economically viable biorefinery. The monitoring of this pretreatment process in terms of delignification and the generation of the fermentation inhibitors acetic acid, furfural, and hydroxymethylfurfural (HMF) is essential in order to adapt the process parameters for a desired outcome and an economical operation. However, traditional wet chemistry methods are time-consuming and not suitable for on-line process monitoring. Therefore, UV-Vis spectroscopy in combination with partial least-squares regression was used for the determination of the concentrations of lignin, acetic acid, furfural, and HMF. Five different data blocks with increasing amounts of impurities were investigated to evaluate the influence of the inevitable impurities on the calibration models. Lignin showed a good prediction accuracy with 95% tolerance intervals between ±0.46 to ±1.6 mg/L for concentrations up to 30 mg/L. Also, the other components could be predicted with a sufficient accuracy for on-line process monitoring. A satisfactory calibration can be obtained with 10 to 20 reference samples valid at process temperatures between 160 °C and 180 °C.This research received no external fundin

Exploitation of Wheat Straw Biorefinery Side Streams as Sustainable Substrates for Microorganisms: A Feasibility Study

Lignocellulosic agricultural side products, like wheat straw, are widely seen as an important contribution to a future sustainable economy. However, optimization of biorefinery processes and exploitation of all side streams are crucial for an economically viable biorefinery. Pretreatment of lignocellulosic raw material, which is necessary for further processing steps, can generate low-value side streams. In this feasibility study, side streams from a liquid hot water (LHW) pretreatment of wheat straw were utilized for the production of polyhydroxybutyrate (PHB) and highly valuable tetraether lipids (TELs). Additional value created by these products can benefit the biorefinery’s economic operation. The utilized wheat straw was pretreated at 120 °C and 170 °C for up to two hours in laboratory and lab scale. The resulting side stream consists mainly of carbohydrates from hemicelluloses and fermentation inhibitors such as acetic acid. In order to achieve a successful production of both products, an acetic acid separation via distillation was necessary. Subsequently, the acetic acid fraction was utilized for the PHB production using cyanobacteria. The carbohydrate-rich fraction was applied in the cultivation of Sulfolobus acidocaldarius and resulted in the successful production of TELs. Both fractions achieved better fermentation yields compared to their corresponding reference media

Production of Micro- and Nanoscale Lignin from Wheat Straw Using Different Precipitation Setups

Micro- and nanosize lignin has recently gained interest due to its improved properties compared to standard lignin available today. As the second most abundant biopolymer after cellulose, lignin is readily available but used for rather low-value applications. Applications for lignin in micro- to nanoscale however, ranging from improvement of mechanical properties of polymer nanocomposites, have bactericidal and antioxidant properties and impregnations to hollow lignin drug carriers for hydrophobic and hydrophilic substances. This research represents a whole biorefinery process chain and compares different precipitation setups to produce submicron lignin particles from lignin containing an organosolv pretreatment extract from wheat straw. A batch precipitation in a stirred vessel was compared with continuous mixing of extract and antisolvent in a T-fitting and mixing in a T-fitting followed by a static mixer. The precipitation in the combination of T-fitting and static mixer with improved precipitation parameters yields the smallest particle size of around 100 nm. Furthermore, drying of particles did not influence the particle sizes negatively by showing decreased particle diameters after the separation process

Influence of Temperature and Lignin Concentration on Formation of Colloidal Lignin Particles in Solvent-Shifting Precipitation

Colloidal lignin particles offer a promising route towards material applications of lignin. While many parameters influencing the formation of these particles in solvent-shifting precipitation have been studied, only a small amount of research on the influence of temperature has been conducted so far, despite it being a major influence parameter in the precipitation of colloidal lignin particles. Temperature influences various other relevant properties, such as viscosity, density, and lignin solubility. This makes investigation of both temperature and lignin concentration in combination interesting. The present work investigates the precipitation at different temperatures and initial lignin concentrations, revealing that an increased mixing temperature results in smaller particle sizes, while the yield is slightly lowered. This effect was strongest at the highest lignin concentration, lowering the hydrodynamic diameter of the particles from 205 to 168 nm. Decreasing the lignin concentration resulted in significantly smaller particles (from 205 to 121 nm at 20 °C mixing temperature) but almost no change in particle yield (between 81.2 and 84.6% at 20 °C mixing temperature). This opens up possibilities for the process control and optimization of lignin precipitation