Catalytic conversion of biomass using solvents derived from lignin

Azadi, Pooya; Carrasquillo‐Flores, Ronald; Pagán-Torres, Yomaira J.; Gürbüz, Elif I.; Farnood, Ramin; Dumesic, James A.

doi:10.1039/c2gc35203f

Cited by 121 publications

(104 citation statements)

References 23 publications

(38 reference statements)

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“…More recently, Azadi et al used a similar method with water as a solvent to produce lignin-derived solvents containing mostly propyl guaiacol and/or propyl syringol (2,6-dimethoxy-4-propylphenol) from poplar. 169 In an interesting example of process integration, this solvent was used as the organic phase in the biphasic reactions to produce furfural, 5-HMF and levulinic acid from biomass. Yan et al improved on these previously developed hydrogenolysis methods by adding phosphoric acid when treating benzeneextracted birch in a water-dioxane mixture in the presence of noble metal catalysts supported on carbon and 4 MPa H 2 at 473 K. 170 With this method, they obtained up to 46%…”

Section: Lignin Monomersmentioning

confidence: 99%

Targeted chemical upgrading of lignocellulosic biomass to platform molecules

2014

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This review presents an overview of the initial targeted chemical processing stages for conversion of lignocellulosic biomass to platform molecules that serve as intermediates for the production of carbonbased fuels and chemicals. We identify four classes of platform molecules that can be obtained in an initial chemical processing step: (i) sugars, (ii) dehydration products, (iii) polyols and (iv) lignin monomers. Special emphasis is placed on reporting and comparing parameters that affect process economics and/or sustainability, including product yields, amount of catalyst used, processing conditions, and product concentrations. We discuss the economic trade-offs associated with choices related to these parameters, depending on the product that is targeted. We also address the effects of real biomass on the ability to recover, recycle, and potentially regenerate catalysts and solvents used in the biomass conversion processes.

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Section: Lignin Monomersmentioning

confidence: 99%

Targeted chemical upgrading of lignocellulosic biomass to platform molecules

2014

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“…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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“…However,t he high pressures (> 5MPa) involved in the CO 2 separation process can lead to safety issues and increased equipment and energy costs, which led us to explore alternative separation solutions. Here, we demonstrate that phenolic solvents such as sec-butylphenol (SBP), nonylphenol (NP), or propyl guaiacol (PG, apotential derivativeo fl ignin) [36,37] can be effective phase modifiers to render the GVL phase insoluble with water while avoiding the pressures associated with liquid CO 2 .T hese solvents lead to improved separation efficiencies, highers ugar concentrations, and, in the case of separation with nonylphenol, ah ydrolysate with reduced toxicity for fermentative organisms even compared with the hydrolysate produced using CO 2 .To further explore the separation between GVL and aqueous sugar solutions that we produced from biomass,d ifferent organic solvents were screened for their abilities to form aG VLorganic phase insoluble in the aqueous solution. Several solvents including alkylphenols such as NP,S BP,o rtert-butylphenol (TBP) formed such ap hase.W ea lso tested PG, ap otential product of lignin hydrogenolysis, [36,37] which successfully formed similarp hases.W et hen explored the effect of increasing the solventc ontento nt he effective recovery of sugars (monomers and oligomers) produced from corn stover in the aqueous phasea nd on the removal of GVL from said aqueous phase (Figure 1).…”

mentioning

confidence: 98%

mentioning

confidence: 98%

“…Several solvents including alkylphenols such as NP,S BP,o rtert-butylphenol (TBP) formed such ap hase.W ea lso tested PG, ap otential product of lignin hydrogenolysis, [36,37] which successfully formed similarp hases.W et hen explored the effect of increasing the solventc ontento nt he effective recovery of sugars (monomers and oligomers) produced from corn stover in the aqueous phasea nd on the removal of GVL from said aqueous phase ( Figure 1). We performed similar experimentsu sing CO 2 for comparison purposes.…”

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Solvent‐Enabled Nonenyzmatic Sugar Production from Biomass for Chemical and Biological Upgrading

et al. 2015

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We recently reported an onenzymatic biomass deconstruction process for producing carbohydrates using homogeneous mixtures of g-valerolactone (GVL) and water as as olvent. Ak ey step in this process is the separation of the GVL from the aqueous phase, enabling GVL recycling and the production of ac oncentrated aqueous carbohydrate solution.I nt his study, we demonstrate that phenolic solvents-sec-butylphenol, nonylphenol, and lignin-derived propylg uaiacol-are effective at separating GVL from the aqueous phase using only small amountso fs olvent (0.5 gp er go ft he originalw ater,G VL, and sugar hydrolysate). Furthermore, using nonylphenol, we produced ah ydrolysate that supported robustg rowth and high yields of ethanol (0.49 gE tOH per gg lucose) at an industrially relevant concentration (50.8 gL À1 EtOH). These resultss uggest that using phenolic solvents could be an interesting solution for separating and/or detoxifying aqueous carbohydrate solutions produced using GVL-based biomass deconstruction processes.Lignocellulosic biomass is emerging as ap otentialr enewable feedstock to replace crude oil as as ource of fuels and commodity chemicals. For this reason,t argeted upgrading routes are being sought to convert biomass to these valuablep roducts. In this context, soluble carbohydrates are an attractive intermediate for biomass upgrading. By weight, structuralp olysaccharides typically represent between 60 and 80 wt %o f lignocellulosic biomass.I na ddition, many chemical [1][2][3][4] and biological [5][6][7][8] processes exist for upgrading carbohydrates to fuels and chemicals.Different strategies exist for deconstructing biomass hemicellulose (a polymer of C 5 sugars; mostly xylose) and cellulose (a polymer of cellobiose, ad imer of glucose) to their soluble counterparts. Concentrated mineral acids such as sulfuric or hydrochloric acid have been used to hydrolyze hemicellulose and cellulose to soluble oligomers almost quantitatively. [9][10][11][12][13] Recently,atwo-stage process consisting of at hermochemical or pretreatment stage followed by enzymatic hydrolysis has been one of the most prominently researched biomass depolymerization methods. [14][15][16][17] Both of these methods can achieve soluble carbohydrate yields upwards of 90 %a nd produce concentrated solutionso fc arbohydrates (> 100 gL À1 ). [10,13,18] Ionic liquids are also attractive solvents for cellulose dissolution and soluble carbohydrate production. [19,20] Although these processes can be used to produce sugars from biomass,t he cost of producing and/or recovering the enzyme, mineral acid, or solvent still represents as ignificant portion of the final process. [21][22][23] For this reason,a lternate systems using significantly less catalyst have also been explored, including dilute acid hydrolysis [24,25] or hydrothermalb iomass depolymerization. [13,[26][27][28] However,a tm ost temperatures (below 510-570 K) and low acid contents( >3%), the rate of sugar degradation and dehydration to furans or other degradation products is of the sam...

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Catalytic conversion of biomass using solvents derived from lignin

Cited by 121 publications

References 23 publications

Targeted chemical upgrading of lignocellulosic biomass to platform molecules

Targeted chemical upgrading of lignocellulosic biomass to platform molecules

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

Solvent‐Enabled Nonenyzmatic Sugar Production from Biomass for Chemical and Biological Upgrading

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