Three different levels of autohydrolysis intensity, expressed as the prehydrolysis (P)-factor, were applied to Eucalyptus globulus wood at a liquor/wood ratio of 5:1. Lignin fractions were isolated from the wood residue as milled wood lignin (MWL), from the hydrolysate by centrifugation (insoluble fraction) and by ethyl acetate extraction (soluble fraction), and from the reactor wall as precipitate. With increasing autohydrolysis duration, a decrease in the content of aliphatic hydroxyl groups and of β-O-4 structures was detected in all lignin fractions, whereas the content of phenolic hydroxyl groups increased in the same order. MWL isolated from wood residue after autohydrolysis at the highest P-factor contained only half the β-O-4 structures contained in native lignin. Molecular weight distribution measurements revealed that fragmentation reactions dominated over condensation reactions in all lignin samples investigated. However, low-molecular-weight lignin dissolved in autohydrolysate exhibited extremely high reactivity towards acid-catalysed condensation reaction, which inevitably leads to the formation of sticky precipitates during storage at elevated temperature under the acid conditions prevailing.

The effect of autohydrolysis of Eucalyptus globulus wood was studied with regard to conditions applied in a prehydrolysis-kraft process on the physico-chemical properties of lignin obtained in both the wood residue and hydrolysate. As a reference, milled wood lignin (MWL) was isolated from native wood and compared to three lignin fractions formed during prehydrolysis: 1) lignin from the wood residue isolated as MWL, 2) lignin precipitated from the prehydrolysate during cooling and separated by centrifugation, and 3) lignin degradation products soluble in the prehydrolysate extracted with ethylacetate. All lignin fractions were subjected to Fourier transform infrared (FTIR) spectroscopy, methoxy group determination, elemental analysis, size exclusion chromatography and quantitative nuclear magnetic resonance (NMR) spectroscopy. The results indicate that extensive lignin degradation occurs during prehydrolysis through homolytic cleavage of the aryl-ether bonds resulting in a substantial molecular weight loss of the residual lignin in the treated wood and in the lignin fractions isolated from the prehydrolysate. The aryl-ether cleavage is coupled with a strong increase in phenolic hydroxyl groups and a decrease in aliphatic hydroxyl groups. Indication for condensation reactions were found by NMR spectroscopy.

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The aim of this study was the experimental demonstration and assessment of a novel lignocellulose biorefinery (LCB) for the integration of beech wood-based products as platform and fine chemicals. The process sequence included organosolv pulping followed by pulp bleaching, hydrothermal conversion of hemicellulose to xylose and its purification, fermentation of xylose to malic acid, and base-catalyzed lignin depolymerization (BCD). The resulting products were dissolving pulp, phenolic BCD-oligomers, and malic acid. The state of the art for these technologies is their experimental proof of concept and validation at a laboratory- and pilot-scale and has a technology readiness level (TRL) of 3–4. By integrating and optimizing the single-process steps into one LCB, the TRL could be increased to 5. Based on the findings of the experimental studies, a LCB converting 50,000 dry metric tonnes ($$ \hat{=} $$=̂ 38.7 MW) of beech wood annually was simulated with Aspen Plus. Mass and energy balances showed that 14,616 dry metric tonnes of dissolving pulp, 5174 dry metric tonnes of BCD-oligomers, and 4077 dry metric tonnes of malic acid annually could be produced. The total energy efficiency is 40.3%. The calculation of specific production costs demonstrated the marketability of dissolving pulp (1350 €/t) and BCD-oligomers (2180 €/t), whereas malic acid (4750 €/t) is not yet competitive. Environmental assessment showed reduced greenhouse gas (GHG) emissions from the production of BCD-oligomers and malic acid and higher GHG emissions from the production of dissolving pulp compared with the reference products. In total, the examined LCB would contribute to the mitigation of global warming.

The solubility and softening behavior of lignin from acid-catalyzed ethanol/water pulping was determined in various ethanol/water solvent mixtures and a process relevant temperature range. Operation conditions for an optimized lignin separation process have been derived from the determined lignin phase behavior. A continuous lignin separation and solvent recovery process  has been developed in lab scale and was successfully up-scaled to a dedicated pilot plant at Fraunhofer CBP (WO2016062676A1). Agglomeration of softened lignin particles and lignin “stickiness” were adjusted by temperature (38–44 °C at 80–120 mbar) and ethanol content of the lignin dispersion (6–9 wt %). In this manner, ethanol recovery by evaporation and lignin particle formation were facilitated simultaneously, which was monitored by inline infrared spectroscopy. The agglomeration behavior of different lignins was monitored via inline particle size analysis. Optimal process conditions resulted in good filterability of the lignin dispersion with average filter cake resistances of 1011 to 1013 m–2 and lignin yields close to 100 wt % of water-insoluble lignin.