The pros and cons of lignin valorisation in an integrated biorefinery

Strassberger, Zea; Tanase, Stéfania; Rothenberg, Gadi

doi:10.1039/c4ra04747h

Cited by 301 publications

(232 citation statements)

References 92 publications

(104 reference statements)

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“…Commercial lignin is fragmented into several niche markets (Zakzeski et al 2010;Strassberger et al 2014;Upton and Kasko 2016 (Tomani 2010;Kouisni et al 2012;Benali et al 2014).…”

Section: Niche Markets For Kraft Mill Biorefinery Productsmentioning

confidence: 99%

Integrating a Biorefinery into an Operating Kraft Mill

Johnson¹,

Hart²

2016

BioResources

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Kraft pulp and paper mills have several advantages for serving the emerging biorefinery industry as a source of raw materials. This review examines technologies for producing liquid biofuels, chemicals, and advanced materials from woody feedstocks to generate new sources of revenue. Market pull comes in part from government policies that drive substitution of petroleum-based products with biobased equivalents. Kraft mills have ample networks to supply feedstocks, whether these are forest residues or byproduct side streams. Pulp mills are well suited to expand sufficiently to accommodate production of value added platform chemicals that are in demand because of brand owner sustainability commitments.

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“…Commercial lignin is fragmented into several niche markets (Zakzeski et al 2010;Strassberger et al 2014;Upton and Kasko 2016 (Tomani 2010;Kouisni et al 2012;Benali et al 2014).…”

Section: Niche Markets For Kraft Mill Biorefinery Productsmentioning

confidence: 99%

Integrating a Biorefinery into an Operating Kraft Mill

Johnson¹,

Hart²

2016

BioResources

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“…Lignocellulosic biomass [1][2] has captured much interest in recent years [3][4][5][6] as a potential cheap and renewable energy source 7 . Lignin, in particular, is a biopolymer 8 (20-30% of biomass by weight 9 ) with high structural heterogeneity that has historically limited its utilization to the fast pyrolysis [10][11] generation of low-grade and volatile bio oil 2 of moderate value 12 .…”

Section: Introductionmentioning

confidence: 99%

Depolymerization Pathways for Branching Lignin Spirodienone Units Revealed with ab Initio Steered Molecular Dynamics

Mar

Kulik

2017

J. Phys. Chem. A

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Lignocellulosic biomass is an abundant, rich source of aromatic compounds, but direct utilization of raw lignin has been hampered by both the high heterogeneity and variability of linking bonds in this biopolymer. Ab initio steered molecular dynamics (AISMD) has emerged both as a fruitful direct computational screening approach to identify products that occur through mechanical depolymerization (i.e., in sonication or ball-milling) and as a sampling approach. By varying the direction of force and sampling over 750 AISMD trajectories, we identify numerous possible pathways through which lignin depolymerization may occur in pyrolysis or through catalytic depolymerization as well. Here, we present eight unique major depolymerization pathways discovered via AISMD for the recently characterized spirodienone lignin branchinglinkage that may comprise around 10% weight of all lignin in some softwoods. We extract representative trajectories from AISMD and carry out reaction pathway analysis to identify energetically favorable pathways for lignin depolymerization. Importantly, we identify dynamical effects that could not be observed through more traditional calculations of bond dissociation energies. Such effects include thermodynamically favorable recovery of aromaticity in the dienone ring that leads to near-barrierless subsequent ether cleavage and hydrogen bonding effects that stabilize newly formed radicals. Some of the most stable spirodienone fragments that reside at most 1 eV above the reactant structure are formed with only 2 eV barriers for C-C bond cleavage, suggesting key targets for catalyst design to drive targeted depolymerization of lignin.2

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“…Meanwhile, lignin is one of the main constituents of these abundant renewable resources, and this cheap feedstock has the potential to aid in the production of liquid fuels and bio-chemicals (Yoshikawa et al 2013;Singh et al 2014;Strassberger et al 2014). However, the efficient conversion of lignin into bio-chemicals is challenging because of the high structural heterogeneity of lignin biopolymers and their recalcitrance to depolymerization.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Depolymerization of Alkali Lignin in Sub- and Super-critical Ethanol

Guo¹,

Liu²,

Tang³

et al. 2017

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The effects of reaction parameters on catalytic depolymerization of alkali lignin in sub-and super-critical ethanol were investigated using a high pressure autoclave, and the liquid oil and solid char products were characterized. The experimental data indicated that Rh catalysis, controlling reaction conditions at ethanol critical temperature (240 ºC) and pressure (7.0 MPa), high ethanol/water ratios (100/0), and the medium reaction time (4 h) enhanced the depolymerization of alkali lignin to liquid oil and decreased the char formation. A gas chromatography/mass spectroscopy (GC/MS) analysis showed that the main compositions of liquid oils were phenols, esters, ketones, and acid compounds, and the supercritical state favored the formation of bio-phenols, but the subcritical state improved the generation of bio-esters. Scanning electron microscopy (SEM) and Fourier transform infrared spectrometer (FTIR) spectra analysis showed that the addition of the Raney/Ni and Rh/C catalysis could inhibit the re-fusion of alkali lignin micron-sized spheres in the supercritical ethanol, which led to an increase in the occurrence of the depolymerization reactions.

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The pros and cons of lignin valorisation in an integrated biorefinery

Abstract: Wood to chemicals is the subject of this short critical review, that outlines the chemical and economic aspects of several short-term and long-term perspectives for the valorisation of lignin to aromatics, polymers and materials.

Cited by 301 publications

References 92 publications

Integrating a Biorefinery into an Operating Kraft Mill

Integrating a Biorefinery into an Operating Kraft Mill

Depolymerization Pathways for Branching Lignin Spirodienone Units Revealed with ab Initio Steered Molecular Dynamics

Catalytic Depolymerization of Alkali Lignin in Sub- and Super-critical Ethanol

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