Catalytic Conversion Of Biomass-derived Carbohydrates Research Articles

Conversion of biomass-derived carbohydrates into 5-hydroxymethylfurfural over sulfonated zirconium/tin mixed-metal metal–organic frameworks in deep eutectic solvents-water based biphasic system

5-hydroxymethylfurfural (5-HMF) is a key platform chemical that can be applied to generate varied value-added products. Herein, the sulfonated zirconium/tin Mixed-Metal metal–organic frameworks (MOFs), Sn/UiO-66-SO3H catalysts were employed for catalytic conversion of biomass-derived carbohydrates (glucose, sucrose, maltose, starch, and cellulose) to 5-HMF in green deep eutectic solvents (DESs)-water based biphasic system. The Sn/UiO-66-SO3H catalysts were prepared by infiltrating Sn4+ into the UiO-66-SO3H via post-synthesis modification. The synthesized catalysts were characterized by PXRD, SEM, FTIR, N2 adsorption–desorption analysis, XPS, ICP-OES, NH3-TPD and Py-FTIR. The synergistic effect of Zr4+ and Sn4+ increased the total acidity and pore size of MOFs, thus promoting the catalytic performance of MOFs towards carbohydrates conversion to 5-HMF. The 24-Sn/UiO-66-SO3H with impregnation of Sn4+ for 24 h presented desired catalytic ability, which resulted in 81.5 % and 41.7 % 5-HMF yields from glucose and cellulose in DES betaine-malic acid–water/MIBK biphasic system, respectively. Moreover, the five-recycling test for 24-Sn/UiO-66-SO3H demonstrated excellent reusability of the prepared catalyst. This study offered a novel sulfonated Mixed-Metal strategy on MOFs in DES betaine-malic acid–water based biphasic system for the production of 5-HMF from biomass-derived carbohydrates.

Direct Catalytic Conversion of Biomass-derived Carbohydrates to Ethyl Levulinate

Abstract: Recently, levulinic acid as an important bio-based platform compound has attracted wide attention, and its potential application value is very high. This article focuses on chem-catalytic produced ethyl levulinate (EL) from biomass-derived carbohydrates (C6 carbohydrates) via multiple reaction pathways, which has an energy density comparable to gasoline and has great potential as a fuel additive. This review focuses on recent examples of the synthesis of EL from various materials using homogenous or heterogeneous catalysts. Special emphasis is placed on the understanding of the reaction mechanism and pathways. This review also summarizes the future opportunities and challenges associated with the applications of EL as a fuel additive and in other fields.

Temperature-responsive Zn-based catalysts for efficient catalytic conversion of biomass-derived carbohydrates to ethyl lactate

Chemical catalytic conversion of biomass-derived sugars to lactic acid has attracted considerable attention due to the cheap, abundant and renewable nature of biomass and its huge potential application in the synthesis of polylactic acid.

Direct conversion of biomass-derived carbohydrates to 5-hydroxymethylfurfural using an efficient and inexpensive manganese phosphate catalyst

Achieving high yields of 5-hydroxymethylfurfural (HMF) from carbohydrates remains a challenge today. With the aim of developing an efficient and inexpensive catalyst for the production of HMF, manganese phosphate (MnPO4) was used as the sole catalyst for the catalytic conversion of biomass-derived carbohydrates into HMF in the H2O/tetrahydrofuran (THF) biphasic reaction system. The effects of various factors, including reaction temperature, reaction time, system, and catalyst dosage on the conversion of carbohydrates to HMF were explored. An impressing HMF yield of 59% was achieved with glucose as a feedstock at 160 °C for 90 min. Meanwhile, up to 44% of HMF was also obtained with microcrystalline cellulose as a feedstock at 170 °C for 120 min. In addition, MnPO4 catalyst also displayed outstanding catalytic activities for the conversion of other biomass-derived carbohydrates including monosaccharides and disaccharides. Combined with the dissolution characteristics of the MnPO4, a possible catalytic mechanism for the conversion of carbohydrates into HMF catalyzed by MnPO4 was proposed. The catalytic approach proposed in this paper exhibited a promising potential for HMF production via optimizing the catalytic process.

Catalytic Conversion of Biomass-Derived Carbohydrates to Methyl Lactate by Acid–Base Bifunctional γ-Al2O3

We report the catalytic conversion of biomass-derived carbohydrates to methyl lactate using metal oxides. The combination of Lewis acid–base sites on γ-Al2O3 is superior to several amphoteric oxides for the production of methyl lactate from both dihydroxyacetone and glucose in methanol. The successful production of methyl lactate from glucose by γ-Al2O3 is attributed to high densities of both acid and base functionalities that are essential for the promotion of the stepwise reaction, which consists of isomerization, retro-aldol, and dehydration reactions.

A structure–activity relationship study using DFT analysis of Bronsted–Lewis acidic ionic liquids and synergistic effect of dual acidity in one-pot conversion of glucose to value-added chemicals

The catalytic conversion of biomass-derived carbohydrates to value-added chemicals, such as 5-hydroxymethylfurfural, levulinic acid, and formic acid, is a commercially important reaction and requires the use of both Lewis and Bronsted acids.

Catalytic Conversion of Biomass-derived Carbohydrates into 5-Hydroxymethylfurfural using a Strong Solid Acid Catalyst in Aqueous γ-Valerolactone

Selective conversion of biomass-derived carbohydrates into 5-hydroxy-methylfurfural (HMF) is of great significance for biomass conversion. In this study, a novel solid Bronsted acid was prepared simply by the copolymerization of paraformaldehyde and p-toluenesulfonic acid and then used to catalyze the conversion of various carbohydrates into HMF in γ-valerolactone-water (GVL/H2O) reaction medium for the first time. The catalyst exhibited strong acidity, good water resistance, and high thermal stability. The present work focuses on the effects of various reaction parameters, including reaction temperature, time, water concentration, solvent, fructose level, and catalyst loading, on fructose dehydration. The catalyst exhibited excellent catalytic performance for HMF production from fructose in GVL and furnished a high HMF yield of 78.1% at 130 °C in 30 min. The recycling experiments suggested that the solid acid catalyst could be recycled at least seven times without a noticeable decrease in the catalytic activity. In addition, an attempt to study the one-step conversion of sucrose, glucose, and cellulose into HMF and furfural was performed using the same catalytic system.

Catalytic conversion of biomass-derived carbohydrates to formic acid using molecular oxygen

Here we report a catalytic process for the efficient production of formic acid (FA) from common carbohydrates via VO2+ formed by dissolving sodium metavanadate in acidic water. The polysaccharides undergo a hydrolysis reaction and an immediate oxidation reaction successively to produce FA in the same reaction system. The hydrolysis reaction decomposes the polymerized structures to produce monosaccharides, which are readily oxidized to FA under catalysis of VO2+. Typically, formic acid mole yields are 64.9% from cellulose and 63.5% from xylan (hemicellulose). The separation of FA from the catalytic system and recycling of the catalyst are demonstrated.

Catalytic conversion of biomass-derived carbohydrates into fuels and chemicals via furanic aldehydes

In recent years, substantial interest has been devoted to the conversion of biomass-derived carbohydrates into furanic aldehydes such as furfural, 5-hydroxymethylfurfural (HMF) and 5-halomethylfurfural, because these products are considered as important versatile intermediates that can be further transformed into a wide variety of high performance fuels and high value-added chemicals. However, low yields and high production costs that are due to the special chemical structures and properties of biomass-derived carbohydrates to a large extent have limited the practical production of furanic aldehydes. Recently, various catalytic conversion strategies have been developed to overcome these limitations. In this review, we systematically summarize and discuss catalytic conversion strategies from the perspective of catalysts and reaction solvents as well as formation mechanisms and influencing factors for the production of furanic aldehydes from biomass-derived carbohydrates. Meanwhile, we also outline the synthesis of furanic aldehyde-based fuels such as 2-methylfuran (MF), 2,5-dimethylfuran (DMF), 5-ethoxymethylfurfural (EMF) and alkanes and chemicals such as levulinic acid (LA), 2,5-diformylfuran (DFF) and 2,5-furandicarboxylic acid (FDCA). Moreover, some potential research orientations are proposed based on the major problems encountered in recent research.

Catalytic conversion of biomass-derived carbohydrates to fuels and chemicals by formation and upgrading of mono-functional hydrocarbon intermediates

Aqueous solutions of sugars and polyols can be converted in a single catalytic process to produce a spontaneously separating organic phase consisting of hydrophobic mono-functional hydrocarbons. The process is shown to be stable for over 2 months time on stream at typical reaction conditions (e.g., 503 K and 18 bar total pressure). The composition and yield of this organic phase can be controlled by adjusting process variables, such as temperature, pressure and space velocity. This organic phase contains primarily mono-functional species such as ketones, alcohols, heterocycles, and organic acids. These oxygenated hydrocarbons can serve as an intermediate platform for the conversion of renewable biomass resources into chemicals and fuels. The organic phase can be separated into individual chemicals or can be upgraded to yield specific classes of chemicals. For example, heterocycles can be separated and used as solvents, additives or blending agents for transportation fuels, while aldol-condensation of the ketones and alcohols can produce long chains species for use as alkane fuels. Alternatively, this platform can be tuned to produce alcohols by reducing the ketone and acid groups. Dehydration of these alcohols produces olefins that have use in either the polymer industry, or as feeds for liquid fuels.