Biorefineries play a vital role in reducing dependence on fossil fuels and addressing global warming concerns. Unfortunately, investment in biorefineries remains limited due to economic sustainability concerns. One approach to enhance the economic viability of biorefineries is by fully utilizing the potential of feedstocks, particularly lignocellulosic biomass, which is commonly used in these processes. Traditional processing methods often alter the lignin portion of biomass, making it unsuitable for further utilization. However, when retained in its native form, lignin can serve as a valuable source of chemicals that contribute to the economic sustainability of biorefineries.
The lignin-first approach, which removes lignin from the cellulosic portion before biofuel conversion, allows for the recovery of value-added chemicals from lignin and enhances the sustainability of biorefineries. One common method for implementing this approach is organosolv, which removes the lignin from biomass. This research developed an organosolv pretreatment method to isolate syringaresinol (S-尾-尾'-S), a lignin-derived dimer with various biomedical and industrial applications, from oak sawdust as the source biomass. The method incorporated a heat treatment step to increase syringaresinol yields, and key treatment parameters were optimized for maximum output. This approach was then applied to other biomass types: hardwood, softwood, and grass. Poplar and hemp were identified as alternative sources of syringaresinol. The method also revealed the presence of several other potential value-added compounds in the biomass types investigated.
Additionally, this research established a linear retention index (LRI) for the gas chromatographic (GC) analysis of 25 common lignin-derived monomers and dimers, which are frequently detected in biomass chromatograms after pretreatments like organosolv. LRI values are independent of column characteristics, enabling unambiguous identification of analytes and ensuring reproducibility in experimental results. These calculated values were validated with a second GC system. The LRI facilitates the identification and confirmation of compounds without the need for mass spectrometric (MS) analysis, allowing for comparison of chromatographic results across multiple GC systems and aiding in the prediction of retention times for these compounds.
While extracting value-added compounds like syringaresinol from biomass is the first step, recovering them from complex reaction mixtures presents additional challenges. This study explored the use of cyclodextrins (CDs) as potential recovery materials for syringaresinol. CDs are conical molecules with a hydrophilic exterior and a hydrophobic cavity, which can selectively capture lignans through guest-host complex interactions. Initial high-performance liquid chromatography (HPLC) analysis with a commercial 尾-CD column revealed that lignans, particularly syringaresinol and pinoresinol interact more strongly with 尾-CD than with most other monomeric lignin decomposition products. Furthermore, the study suggested that 纬-CD might be a better recovery material for syringaresinol compared to 尾-CD. To test this hypothesis, a modified frontal analysis continuous capillary electrophoresis (FACCE) method was developed and validated as an inexpensive, simple approach to estimate the binding constants of lignans to CDs. The FACCE method provided insights into the interactions between lignans and CDs, facilitating the selection of the potentially suitable CD-type for recovery.
