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Catalyst deactivation resulting from the hydrothermal leaching of sulfonic acid residues and the deposition of carbonaceous residues was studied using condensed phase flow reactor experiments along...

The use of polar aprotic solvents in acid-catalyzed biomass conversion reactions can lead to improved reaction rates and selectivities. We show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts, specifically chlorides. Reaction kinetics studies of the Brønsted acid-catalyzed dehydration of fructose to hydroxymethylfurfural (HMF) show that the use of catalytic concentrations of chloride salts leads to a 10-fold increase in reactivity. Furthermore, increased HMF yields can be achieved using polar aprotic solvents mixed with chlorides. Ab initio molecular dynamics simulations (AIMD) show that highly localized negative charge on Cl− allows the chloride anion to more readily approach and stabilize the oxocarbenium ion that forms and the deprotonation transition state. High concentrations of polar aprotic solvents form local hydrophilic environments near the reactive hydroxyl group which stabilize both the proton and chloride anions and promote the dehydration of fructose., Despite the potential advantages of using polar aprotic solvents for biomass upgrading reactions, fundamental understanding of these solvation effects is limited at present. Here, the authors show that further increases in catalyst performance in polar aprotic solvents can be achieved through the addition of inorganic salts.

The use of organic solvents in biomass conversion reactions can lead to high rates and improved selectivities. Here, we elucidate the effects of organic solvent mixtures with water on the kinetics of acid-catalysed dehydration reactions of relevance to biomass conversion. Based on results from reaction kinetics studies, combined with classical and ab initio molecular dynamics simulations, we show that the rates of acid-catalysed reactions in the liquid phase can be enhanced by altering the extents of solvation of the initial and transition states of these catalytic processes. The extent of these effects increases as the number of vicinal hydroxyl or oxygen-containing groups in the reactant increases, moving from an alcohol (butanol), to a diol (1,2-propanediol), to a carbohydrate (fructose). We demonstrate that the understanding of these solvation effects can be employed to optimize the rate and selectivity for production of the biomass platform molecule hydroxymethylfurfural from fructose.

High-resolution magic angle spinning (HR-MAS) NMR spectroscopy was used to study the effect of mixed solvent systems on the acidity at the solid–liquid interface of solid acid catalysts. A method was developed that can exploit benefits of both solution and solid-state NMR (SSNMR) by wetting porous solids with small volumes of liquids (

The combination of chemical and biological catalysis enables the production from biomass of coumarin and dihydrocoumarin (DHC), opening new routes to the formation of fine chemicals and pharmaceutical building blocks. Each of these products requires the hydrogenation of 4-hydroxycoumarin (4HC) to 4-hydroxydihydrocoumarin (4HDHC), which, in turn, requires the reduction of an unsaturated C–C bond in the presence of an aromatic ring. Using in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, we show that reaction at 348 K over monometallic Pd catalysts leads to the partial reduction of the aromatic ring in 4HC, obtaining 93% selectivity for C═C bond hydrogenation at 82% 4HC conversion and with a low turnover frequency (TOF). Decreasing the Pd dispersion from 70% to 6% not only leads to an increase in the rate of 4HC hydrogenation, but it also leads to an increase in the rate of overhydrogenation. However, the formation of bimetallic PdAu nanoparticles inhibits the overhydro...

Reaction kinetics were studied to quantify the effects of water on the conversion of hydroxymethylfurfural (HMF) in THF over Cu/γ-Al2 O3 at 448 K using molecular H2 as the hydrogen source. We show that low concentrations of water (5 wt %) in the THF solvent significantly alter reaction rates and selectivities for the formation of reaction products by hydrogenation and hydrogenolysis processes. In the absence of water, HMF was converted primarily to hydrogenolysis products 2-methyl-5-hydroxymethylfuran (MHMF) and 2,5-dimethylfuran (DMF), whereas reactions carried out in THF-H2 O mixtures (THF/H2 O=95:5 w/w) led to the selective production of the hydrogenation product 2,5-bis(hydroxymethyl)furan (BHMF) and inhibition of HMF hydrogenolysis.

Furfuryl alcohol in high concentrations (1 M) was hydrolyzed to levulinic acid in high yields (>70%) using H-ZSM-5 zeolite as the catalyst in monophasic tetrahydrofuran (THF)–water solvent systems. Reaction kinetics studies using H-ZSM-5 were carried out, and combined with results obtained for other Bronsted acid catalysts, we suggest that the structural properties of H-ZSM-5, in conjunction with increased reaction performance using the polar aprotic solvent THF, are effective for furfuryl alcohol hydrolysis to levulinic acid while inhibiting furfuryl alcohol polymerization reactions. In addition, on the basis of results obtained for a wide range of THF–H2O solvent systems (19:1–1:2 w/w), we suggest that the hydrophobic nature of H-ZSM-5 alters the internal solvent microenvironment within the zeolite framework, allowing for high levulinic acid yields, even at low THF solvent concentrations (e.g., 1:2 THF–H2O w/w).

Replacing petroleum by biomass can be economically feasible by generating revenue from the three primary biomass constituents., The production of renewable chemicals and biofuels must be cost- and performance- competitive with petroleum-derived equivalents to be widely accepted by markets and society. We propose a biomass conversion strategy that maximizes the conversion of lignocellulosic biomass (up to 80% of the biomass to useful products) into high-value products that can be commercialized, providing the opportunity for successful translation to an economically viable commercial process. Our fractionation method preserves the value of all three primary components: (i) cellulose, which is converted into dissolving pulp for fibers and chemicals production; (ii) hemicellulose, which is converted into furfural (a building block chemical); and (iii) lignin, which is converted into carbon products (carbon foam, fibers, or battery anodes), together producing revenues of more than $500 per dry metric ton of biomass. Once de-risked, our technology can be extended to produce other renewable chemicals and biofuels.

Reaction kinetics were studied to quantify the effects of polar aprotic organic solvents on the acid-catalyzed conversion of xylose into furfural. A solvent of particular importance is g-valerolactone (GVL), which leads to signifi- cant increases in reaction rates compared to water in addition to increased product selectivity. GVL has similar effects on the kinetics for the dehydration of 1,2-propanediol to propanal and for the hydrolysis of cellobiose to glucose. Based on results obtained for homogeneous Bronsted acid catalysts that span a range of pKa values, we suggest that an aprotic organic solvent affects the reaction kinetics by changing the stabiliza- tion of the acidic proton relative to the protonated transition state. This same behavior is displayed by strong solid Bronsted acid catalysts, such as H-mordenite and H-beta. The use of organic solvents is pervasive in the chemical industry, and recently it has been shown that organic solvents are beneficial in the chemical conversion of lignocellulosic biomass. (1-3) One such solvent is g-valerolactone (GVL), which can be produced from biomass and displays significant improvements in reaction performance for biomass conver- sion reactions compared to conversion in aqueous media, such as increased catalytic activity and higher selectivity to desired reaction products. (2, 3) Furthermore, we have reported that the simultaneous conversion of hemicellulose and cellulose can be achieved using GVL as a solvent in a single reactor, eliminating the need for pretreatment and/or sepa- ration steps. (4) Recently, we have taken advantage of accel- erated rates of cellulose and hemicellulose deconstruction in GVL-H2O solvent mixtures to develop a processing strategy to produce streams of C5 and C6 sugars (e.g., 130 g l � 1 ) from biomass. (5) Other polar aprotic solvents, such as g-lactones and tetrahydrofurans, have also shown comparable benefits to GVL in biomass conversion processes. (3) Herein, we report the effects of GVL and other polar aprotic solvents on acid-catalyzed biomass conversion reac- tions using acid catalysts that span a range of pKa values. The liquid-phase dehydration of xylose to furfural is catalyzed by Bronsted acids and serves as a probe reaction in the present study. We compare the reactivity trends displayed by these homogeneous acid catalysts in the liquid phase with the performance of solid acid catalysts, the latter of which have been shown to span a range of catalytic activities for the gas

The use of γ-valerolactone as solvent for acid-catalyzed biomass hydrolysis reactions increases reaction rates compared to reactions carried out in water. In addition, a low apparent activation energy for biomass hydrolysis and a higher value for monosaccharide conversion are displayed using GVL as solvent, leading to favorable energetics for monosaccharide production from biomass.

The production of furfural from the C5 monosaccharides xylose, arabinose and ribose, as well as from real biomass (corn fiber), was studied using H-Beta zeolite as catalyst in a monophasic system with the biomass-derived solvent, gamma-valerolactone. Due to the combination of Bronsted and Lewis acid sites on this catalyst (Bronsted:Lewis ratio = 1.66), H-Beta acts as a bifunctional catalyst, being able to isomerize (Lewis acid) and dehydrate (Bronsted acid) monosaccharides. The combination of Lewis and Bronsted acid functionality of H-Beta was shown to be effective for the isomerization of xylose and arabinose, followed by dehydration. While no advantages were found in the conversion of xylose, higher furfural yields were achieved from arabinose, using H-Beta, 73 %, compared to sulfuric acid (44 %) and Mordenite (49 %). The furfural yields from corn fiber for H-Beta, H-Mordenite and sulfuric acid were 62, 44, and 55 %, respectively, showing that H-Beta is particularly effective for conversion of this biomass feedstock composed of 45 wt% hemicellulose, of which 66 % is xylose and 33 % arabinose.

Cellulose was converted with high yield (69%) to levulinic acid (LA) using Amberlyst 70 as the catalyst and using a solution of 90 wt% gamma-valerolactone (GVL) and 10 wt% water as the solvent, compared to the low yield of 20% obtained in water. The LA was upgraded to GVL without any neutralization or purification steps due to the solubilization of humins by the GVL solvent. High LA yields (54%) were also obtained from real biomass (corn stover).

High yields of HMF from glucose can be achieved using biomass-derived solvents and a combination of solid Lewis and Bronsted catalysts in a salt-free reaction system. The HMF produced in this system can be oxidized to FDCA or hydrogenated to DMF, both being high-value chemicals.

Using gamma-valerolactone (GVL) as solvent, the cellulosic fraction of lignocellulosic biomass can be converted into levulinic acid (LA), while at the same conditions the hemicellulose fraction can be converted into furfural. This process allows for the conversion of hemicellulose and cellulose simultaneously in a single reactor, thus eliminating pre-treatment steps to fractionate biomass and simplifying product separation.

Carbon−Carbon Bonds in Aromatic-Containing Platform Molecules” Thomas J. Schwartz,†,‡ Spencer D. Lyman,‡ Ali Hussain Motagamwala,‡,§ Max A. Mellmer,‡,§ and James A. Dumesic*,‡,§ †Department of Chemical and Biological Engineering, University of Maine, Orono, Maine 04469, United States ‡Department of Chemical and Biological Engineering, University of Wisconsin−Madison, Madison, Wisconsin 53706, United States DOE Great Lakes Bioenergy Research Center, University of Wisconsin−Madison, Madison, Wisconsin 53726, United States