Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds

Das, Lalitendu; Li, Mi; Stevens, Joseph; Li, Wenqi; Pu, Yunqiao; Ragauskas, Arthur J.; Shi, Jian

doi:10.1021/acssuschemeng.8b01763

Title: Characterization and Catalytic Transfer Hydrogenolysis of Deep Eutectic Solvent Extracted Sorghum Lignin to Phenolic Compounds

Journal Article · Wed Jun 06 00:00:00 EDT 2018 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.8b01763· OSTI ID:1463981

Das, Lalitendu ^[1]; Li, Mi ^[2]; Stevens, Joseph ^[1]; Li, Wenqi ^[1]; Pu, Yunqiao ^[3];

^[4];

^[1]

Univ. of Kentucky, Lexington, KY (United States). Biosystems and Agricultural Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. of Biological Science. BioEnergy Science Center. Center for BioEnergy Innovation. Biosciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. of Biological Science. BioEnergy Science Center. Center for BioEnergy Innovation. Biosciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. of Biological Science. BioEnergy Science Center. Center for BioEnergy Innovation. Biosciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering. Inst. of Agriculture. Dept. of Forestry, Wildlife, and Fisheries. Center for Renewable Carbon

Deep eutectic solvent (DES) is intrinsically cheaper than many ionic liquids (ILs) due to low precursor cost, simple synthesis, and improved recyclability. Meanwhile, DES can be as effective as ILs toward dissolving lignin from plant materials. However, the lignin depolymerization mechanism in DES, the structural and chemical properties of DES-extracted lignin (DES-EL), and the possible valorization pathways of DES-EL toward value-added products were not well understood. This paper aims to characterize the lignin streams from DES (1:2 choline chloride:lactic acid) treated sorghum and further upgrade the extracted lignin to phenolic compounds. As revealed by HSQC, ¹³C, and ³¹P NMR analysis, DES cleaved nearly all ether linkages in native lignin, resulting in significant size reduction. We further catalytically upgraded DES-EL to phenolic compounds via catalytic transfer hydrogenolysis in the presence of isopropyl alcohol. Among the three tested catalysts (Ru/C, Pd/C, and Pt/C), Ru/C proved the most effective in deconstructing DES-EL, with oil, char, and gas yields of 36.3, 46.4, 17.3 wt %, respectively. Major lignin monomeric products in the oil were phenol, 4-ethylphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-propylphenol, and 4-hydroxy-benzenepropanoic acid. Finally, this study provides a mechanistic understanding of lignin depolymerization in DES and demonstrates a possible way to catalytic upgrading of DES-EL to low molecular weight phenolic compounds.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Kentucky, Lexington, KY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; 1355438; 1632854

OSTI ID:: 1463981

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 8; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 46 works

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