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Fractionation of lignocellulosic biomass to produce uncondensed aldehyde-stabilized lignin

Abstract

Lignin is one of the most promising sources of renewable aromatic hydrocarbons. Current methods for its extraction from lignocellulosic biomass—which include the kraft, sulfite, and organosolv processes—result in the rapid formation of carbon–carbon bonds, leading to a condensed lignin that cannot be effectively depolymerized into its constituent monomers. Treatment of lignocellulosic biomass with aldehydes during lignin extraction generates an aldehyde-stabilized lignin that is uncondensed and can be converted into its monomers at near-theoretical yields. Here, we outline an efficient, reproducible, and scalable process for extracting and purifying this aldehyde-stabilized lignin as a solid, which can easily be re-dissolved in an organic solvent. Upon exposure to hydrogenolysis conditions, this material provides near-theoretical yields of aromatic monomers (~40–50% of the Klason lignin for a typical hardwood). Cellulose and hemicellulose are also efficiently fractionated. This protocol requires 6–7 h for the extraction of the stabilized lignin and a basic proficiency in synthetic chemistry.

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Fig. 1: Chemical pathways during lignin extraction and valorization.
Fig. 2: The products of the propionaldehyde fractionation procedure (Steps 35–83).
Fig. 3: Mass balances during the aldehyde fractionation of lignocellulosic biomass, as performed on 2018 birch wood.
Fig. 4: Hydrogenolysis data for the formaldehyde and propionaldehyde-stabilized lignins as compared with the direct hydrogenolyses of the feedstock biomass.
Fig. 5: The formaldehyde biomass fractionation procedure (Steps 1–34).
Fig. 6: The propionaldehyde biomass fractionation procedure (Steps 35–83).

Data availability

The exemplary data that were produced in support of the described procedures are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (starting grant: CATACOAT, no. 758653), the Swiss National Science Foundation through grant PYAPP2_154281, and the École Polytechnique Fédérale de Lausanne. This work was also accomplished within the framework of the Swiss Competence Center for Bioenergy Research (SCCER-BIOSWEET). We thank L. Menin and D. Ortiz of the SSMI mass spectrometry facility at EPFL for their assistance. We thank W. Lan for helpful discussions during the preparation of the manuscript, especially for the structural assignments of the lignin NMRs.

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Authors and Affiliations

Authors

Contributions

M.T.A. and G.R.D. developed and performed the aldehyde-based fractionations, cellulose hydrolyses, and lignin hydrogenolyses. M.T.A., G.R.D., and Y.M.Q.-S. performed the cellulose compositional analyses. G.R.D. performed the biomass compositional analyses. The project was conceived of by M.T.A., G.R.D., and J.S.L. and supervised by J.S.L. All authors participated in the preparation of the manuscript.

Corresponding author

Correspondence to Jeremy S. Luterbacher.

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Competing interests

The authors declare competing interests. J.S.L. is an inventor on a European patent application (EP16165180.7) that was submitted by EPFL and covers methods for producing lignin monomers from biomass during biomass depolymerization.

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Journal peer review information: Nature Protocols thanks Robert Brown and other (anonymous) reviewer(s) for their contribution to the peer review of this work.

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Related links

Key references using this protocol

Shuai, L. et al. Science. 354, 329–333 (2016): http://science.sciencemag.org/content/354/6310/329

Lan, W. et al. Angew. Chem. Int. Ed. 57, 1356–1360 (2018): https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.201710838

Integrated supplementary information

Supplementary Figure 1 Data for the unextracted and extracted propionaldehyde-stabilized lignins compared with the direct hydrogenolyses of the feedstock biomass.

These two charts compare the monomer yields from the hydrogenolysis of the raw biomass (Direct Hydrogenolysis), propionaldehyde-stabilized lignin derived from unextracted wood, and propionaldehyde-stabilized lignin derived from extracted wood for two biomass sources: 2018 Birch and 2018 Beech. The direct hydrogenolysis represents the highest possible yield (% (wt/wt)) of monomers for these biomass sources and was performed on biomass that had not been extracted or dried. The difference in yields between the extracted and unextracted propionaldehyde protected lignins is approximately 1% on a Klason Lignin Weighted Basis. Each data point represents one experiment.

Supplementary Figure 2 HSQCs in DMSO-d6 of the formaldehyde-stabilized lignins.

(a) 2018 birch wood and (b) 2018 beech wood.

Supplementary Figure 3 HSQCs in DMSO-d6 of the propionaldehyde-stabilized lignins.

(a) 2018 birch wood and (b) 2018 beech wood.

Supplementary Figure 4

1H-NMR of diformylxylose in CDCl3.

Supplementary Figure 5

13C-NMR of diformylxylose in CDCl3.

Supplementary Figure 6

HSQC of diformylxylose in CDCl3.

Supplementary Figure 7

1H-NMR in CDCl3 of diformylxylose isolated from the 2018 birch wood using the formaldehyde fractionation protocol.

Supplementary Figure 8

1H-NMR in CDCl3 of diformylxylose isolated from the 2018 beech wood using the formaldehyde fractionation protocol.

Supplementary Figure 9

1H-NMR of (2R,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 10

13C-NMR of (2R,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 11

HSQC of (2R,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 12

1H-NMR of (2S,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine.dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 13

13C-NMR of (2S,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine.dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 14

HSQC of purified (2S,3aR,3bS,5R,7aR,8aR)-2,5-diethyltetrahydro-7H-[1,3]dioxolo[4′,5′:4,5]furo[3,2-d][1,3]dioxine.dioxine (dipropylxylose) in CDCl3.

Supplementary Figure 15

1H-NMR in CDCl3 of dipropylxylose (mixture of isomers) isolated from the 2018 birch wood using the propionaldehyde fractionation protocol.

Supplementary Figure 16

1H-NMR in CDCl3 of dipropylxylose (mixture of isomers) isolated from the 2018 beech wood using the propionaldehyde fractionation protocol.

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Talebi Amiri, M., Dick, G.R., Questell-Santiago, Y.M. et al. Fractionation of lignocellulosic biomass to produce uncondensed aldehyde-stabilized lignin. Nat Protoc 14, 921–954 (2019). https://doi.org/10.1038/s41596-018-0121-7

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