No abstract

Objective of this study was the investigation on the up-scaling of base-catalyzed depolymerization (BCD) of lignin to pilot plant dimension. The cleavage process was carried out in dilute alkaline solution at temperatures up to 340˚C and a pressure of 25 MPa in a continuously operated tubular flow reactor with throughputs up to 20 kg/h. Investigations included the proof of the feasibility of the scale-up as well as a parameter study on the cleavage of hardwood Organosolv lignin and softwood Kraft lignin within the established pilot plant. Yields and molecular compositions of the isolated product fractions BCD-oil (liquid phenolic fraction) and BCD-oligomers (solid phenolic fraction) are similar to those described in technical lab scale, showing a good scalability. Here, BCD-oils rich in phenolic monomers such as guaiacol, catechol and/or syringol were obtained with a content of up to 13.3 wt% and 14.5 wt% from Organosolv lignin and Kraft lignin, respectively. Formation of BCDoligomers strongly depends on temperature and residence times within the reactor.

Bio-based phenolic compounds available from lignin are promising candidates for industrial application, e.g., within polymer resins or as biogenic fuel substitutes. Among numerous conversion methods for the valorization of lignin, the base-catalyzed depolymerization (BCD) has considerable advantages with respect to other processes. By this method, lignin and lignin-containing biorefinery streams can be catalytically transferred to valuable, defined products with tailored specifications. Continuous process operation allows conversions at short residence times and, thus, enables its industrial implementation more easily due to economic reasons. This review reflects the development in the field of BCD on various types of lignin. A historical overview will be given and the principal application of the method is shown. Challenges for operations are addressed, mainly to the development of efficient and selective methods for product separation and purification of the alkylphenolic moieties and the reduction of char formation during the process. An outlook will be given by showing trends and perspectives, especially in the field of industrial applications. Here, hydrotreatment methods for refining BCD intermediates for fuel and platform chemical production are shown. Furthermore, the application of BCD for the conversion of woody biomass and black liquor is discussed.

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 extraction and characterization of defined and carboxyl-rich oligomeric lignin fragments with narrow molecular weight distribution is presented herein. With regard to the well-known pulp bleaching process, oxidative lignin depolymerization was investigated using hydrogen peroxide in an aqueous alkaline solution (i.e., at T = 318 K, t = 1 h) and subsequent selective fractionation with a 10/90 (v/v) acetone/water mixture. While the weight average molecular weight (MW) of lignin in comparison to the starting material was reduced by 82% after oxidation (T = 318 K, t = 1 h, clignin = 40 g L−1, cH2O2 = 80 g L−1, cNaOH = 2 mol L−1) and subsequent solvent fractionation (T = 298 K, t = 18 h, ccleavage product = 20 g L−1), the carboxyl group (–COOH) content increased from 1.29 mmol g−1 up to 2.66 mmol g−1. Finally, the successful scale-up of this whole process to 3 L scale led to gram amounts (14% yield) of oligomeric lignin fragments with a MW of 1607 g mol−1, a number average molecular weight (MN) of 646 g mol−1, a narrow polydispersity index of 3.0, and a high –COOH content of 2.96 mmol g−1. Application of these oligomeric lignin fragments in epoxy resins or as adsorbents is conceivable without further functionalization.