DOE OSTI · 3020954
Functionalized benzylamines from commercial kraft lignin
Abstract
Benzylamines are key intermediates in pharmaceuticals, agrochemicals, and polymers, but their conventional production relies on benzyl chloride - a petroleum-derived compound with high toxicity and energy demands. Lignin, accounting for up to 30% of plant biomass, is the largest renewable source of aromatic carbon on Earth. However, its highly complex and recalcitrant structure poses a major barrier to efficient conversion into high-value chemicals. Here, in this study, we developed a catalytic approach to convert commercial kraft lignin into phenolic benzylamines through selective depolymerization and subsequent functionalization. We systematically evaluated the effects of three alcohol solvents, formic acid (FA), and a ruthenium-on‑carbon (Ru/C) catalyst on monophenol yield and selectivity. Up to 6.5 wt% monophenol yield was achieved using methanol (MeOH), FA, and Ru/C at 300 °C for 2 h. Quantum thermodynamic simulations based on the COSMO-RS model confirmed the superior solvation and reactivity of the MeOH + FA system, rationalizing observed product yield. The purified monophenolic products, primarily guaiacol and alkyl guaiacols, were then converted into functionalized benzylamines with >90% yield via a multicomponent Mannich reaction under mild conditions. Techno economic analysis (TEA) and life cycle assessment (LCA) underscore the importance of improving lignin depolymerization yields and expanding biorefinery scale. Solvent-only configurations outperform other options in both cost and emissions, with the methanol-only case performing the best ($\$$105 /kg and 26 kg CO 2e /kg) at a large-scale facility. This study establishes a scalable, bio-based pathway for producing benzylamines from commercial kraft lignin, advancing lignin valorization and offering a sustainable alternative to produce petrochemical-based benzylamines.
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Dou, Chang [Lawrence Berkeley National Laboratory (LBNL), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)], Yang, Minliang [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); North Carolina State University, Raleigh, NC (United States)], Kumar, Nikhil [Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)], Aguilar, Rolin A. [Lawrence Berkeley National Laboratory (LBNL), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States); Stanford University, CA (United States)], Hitt, Addison J. [Lawrence Berkeley National Laboratory (LBNL), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Queens University of Charlotte, NC (United States)], Gonzalez, Griffen [Queens University of Charlotte, NC (United States)], Scown, Corinne D. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); University of California, Berkeley, CA (United States)], Sale, Kenneth L. [Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000242698940), Choudhary, Hemant [Joint BioEnergy Institute (JBEI), Emeryville, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)] (ORCID:0000000328473080), Socha, Aaron M. [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Queens University of Charlotte, NC (United States); Graz University of Technology (Austria)], Sun, Ning [Lawrence Berkeley National Laboratory (LBNL), Emeryville, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)]. 2026-02-23. Functionalized benzylamines from commercial kraft lignin. https://doi.org/10.1016/j.cej.2026.174287
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