Biomass-derived Glucose Research Articles

Manganese-Biochar Catalyst for Sustainable Glycolic Acid Production from Biomass-Derived Glucose and Oligosaccharides

Manganese-Biochar Catalyst for Sustainable Glycolic Acid Production from Biomass-Derived Glucose and Oligosaccharides

Modular synthesis of pyrrole-fused heterocycles via glucose-mediated nitro-reductive cyclization.

A novel biomass-derived glucose-mediated one-pot multicomponent nitro-reductive cyclization method is presented for the direct synthesis of diverse pyrrole-fused heterocycles. The process involves two-component reactions of alkyl (NH)-pyrrole-2-carboxylates and 2-fluoronitroarenes, yielding pyrrolo[1,2-a]quinoxalin-4(5H)-ones, as well as three-component reactions utilizing (NH)-pyrroles, nitroarenes, and DMSO as carbon sources, resulting in various pyrrolo[1,2-a]quinoxaline derivatives. High yields were achieved with broad substrate scope and gram-scale synthesis capability, including pharmaceuticals featuring pyrroloquinoxaline scaffolds. The method's key innovation lies in enabling three or four reactions in a single-pot setup, previously unexplored in pyrrole chemistry. The simplicity of nitro group reduction by biomass-derived glucose ensures practical safety during scale-up, while mechanistic insights from control experiments reveal a new paradigm in pyrrole chemistry. The tandem process demonstrates low PMI values and high step and atom economies, aligning well with green chemistry principles.

Design of a supply chain network for chemicals from biomass using green electrochemistry

Increasing concern about the environmental impact of industrial activities has prompted a shift to renewable energy sources and the development of environmentally conscious supply chains. In this regard, electrochemistry has shown promise for converting biomass into specialty chemicals in distributed facilities that exploit renewable energy resources. To examine the impact of electrochemistry technology on optimal supply chain configuration, we formulate a mixed-integer linear programming model to optimize the locations and capacities of distributed facilities for converting biomass to chemicals. The economic objective of the supply chain design model is to minimize the totalannualcost of producing chemicals from biomass-derived glucose and delivering them to market. To analyze the trade-off between environmental andeconomicconsiderations, we also consider an environmental objective of minimizing greenhouse gas (GHG) emissions. The results of a US case study indicate that, while cost is minimized by constructing one large facility, GHG emissions are lowered by a distributed configuration. Varying the setting of a process design parameter expands the Pareto frontier along which decision-makers can choose a configuration according to their preferences between economic and environmental criteria.

Nano Metal Oxide Frameworks (NOF): Development of New Heterogeneous Catalyst for the Synthesis of Furan Derivatives from Glucose

A surface modification approach has prepared a nanostructured organic framework connecting two metal oxide NPs. The surface modifier attached two metal oxide NPs <em>via</em> molecular interaction to generate modular structures of fiber, rod, or sponge materials. Thus, obtained hybrid systems have been confirmed through FT-IR, TGA, PXRD, and SEM. Metal oxides such as Fe<sub>3</sub>O<sub>4</sub> and MgO generated mixed materials via the surface modification approach. Thus, obtained materials have been successfully used to dehydrate biomass-derived glucose. The products HMF and subsequently partially oxidized product DFF are considered to be valuable compounds not only in fuel technology but also in the pharmaceutical industry.

Low pH Stress Enhances Gluconic Acid Accumulation with Enzymatic Hydrolysate as Feedstock Using Gluconobacter oxydans

Gluconic acid has been increasingly in demand in recent years due to the wide applications in the food, healthcare and construction industries. Plant-derived biomass is rich in biopolymers that comprise glucose as the monomeric unit, which provide abundant feedstock for gluconic acid production. Gluconobacter oxydans can rapidly and incompletely oxidize glucose to gluconic acid and it is regarded as ideal industrial microorganism. Once glucose is depleted, the gluconic acid will be further bio-oxidized to 2-ketogluconic acid by Gluconobacter oxydans. The endpoint is difficult to be controlled, especially in an industrial fermentation process. In this study, it was found that the low pH environment (2.5~3.5) could limit the further metabolism of gluconic acid and that it resulted in a yield over 95%. Therefore, the low pH stress strategy for efficiently producing gluconic acid from biomass-derived glucose was put forward and investigated with enzymatic hydrolysate. As a result, 98.8 g/L gluconic acid with a yield of 96% could be obtained from concentrated corncob enzymatic hydrolysate that initially contained 100 g/L glucose with 1.4 g/L cells loading of Gluconobacter oxydans. In addition, the low pH stress strategy could effectively control end-point and decrease the risk of microbial contamination. Overall, this strategy provides a potential for industrial gluconic acid production from lignocellulosic materials.

Chemocatalytic Conversion of Lignocellulosic Biomass to Ethanol: A Mini-Review

Ethanol has been widely used as a clean fuel, solvent, and hydrogen carrier. Currently, ethanol is generally produced through fermentation of starch- and sugarcane-derived sugars (e.g., glucose and sucrose) or ethylene hydration. Its production from abundant and inexpensive lignocellulosic biomass would facilitate the development of green and sustainable society. Biomass-derived carbohydrates and syngas can serve as important feedstocks for ethanol synthesis via biological and chemical pathways. Nevertheless, the biological pathway for producing ethanol through biomass-derived glucose fermentation has the disadvantages of long production period and carbon loss. These issues can be effectively mitigated by chemocatalytic methods, which can readily convert biomass to ethanol in high yields and high atomic efficiency. In this article, we review the recent advances in chemocatalytic conversion of lignocellulosic biomass to ethanol, with a focus on analyzing the mechanism of chemocatalytic pathways and discussing the issues related to these methods. We hope this mini-review can provide new insights into the development of direct ethanol synthesis from renewable lignocellulosic biomass.

Preparation of Metal-Loaded ZSM-5 Zeolite Catalyst and Its Catalytic Effect on HMF Production from Biomass.

This research work presented the preparation of metal-loading ZSM-5 zeolite catalyst by loading Cu and Cr ions into the ZSM-5 zeolite particles using ion exchange method. Technical conditions of ion exchange processes were investigated to find suitable process for preparation of modified zeolite. The as-obtained zeolite catalyst was then applied for the transformation reaction of biomass-derived glucose into 5-hydroxymethyl furfural (HMF). Glucose hydrolysate that achieved from enzymatic hydrolysis of rice straw was used as feedstock for transformation reaction using Cu-Cr/ZSM-5 catalyst. This metal-loading zeolite exhibited good catalytic activity for lignocellulosic conversion to HMF, a valuable renewable green chemical. The content of loading metals in the zeolite catalyst affected significantly on the HMF yield. Moreover, the influence of transformation conditions such as solvent, temperature, catalyst dosage, and reaction time was investigated. According to the results, the optimum condition leading to the highest yield of HMF of 49.5 ± 0.5% was established. The as-prepared Cu-Cr/ZSM-5 zeolite catalyst showed impressive performance and can be considered a promising catalyst for the transformation of biomass-derived glucose to HMF.

Exploration of lower critical solution temperature DES in a thermoreversible aqueous two-phase system for integrating glucose conversion and 5-HMF separation

With the deepening of the research on the conversion of cellulose biomass to furfural, there is no green and efficient method to separate sugars and 5-HMF. This study utilized a thermoreversible aqueous two-phase system (ATPS) coupled with tetrabutylammonium bromide ([N4444]Br)- based deep eutectic solvents (DES) and inorganic salts for separating glucose and 5-HMF. The thermal characteristics of DESs were analyzed by thermogravimetry (TGA) and differential scanning calorimetry (DSC). The thermoreversible phase behavior of ATPS was determined by phase diagram. Furthermore, the process factors were optimized, such as the type and concentration of DES and phosphate, the temperature, and the time of ATPS were investigated, to maximize the separation of glucose and 5-HMF. Finally, the ATPS was a successful integrated catalytic reaction of glucose involving CrCl3 and 5-HMF separation. The results showed that the ATPS consist of 30 wt% [N4444]Br-EG and 25 wt% K2HPO4 had the most efficient extraction rate, 5-HMF reached 96.0 ± 0.6%, and mainly existed in the DES phase, while glucose was enriched in salt phase, and the extraction rate reached 99.9 ± 0.03%. And the 5-HMF yield reached 25.6 ± 1.1% in the production separation integrated platform. This thermoreversible ATPS may provide a guide for the effective extraction of furfural from biomass-derived glucose.

Catalytic Transformation of Biomass-Derived Glucose by One-Pot Method into Levulinic Acid over Na-BEA Zeolite

This article presents the results of the conversion of biomass-based glucose to levulinic acid (LA) with the use of Na-BEA commercial zeolite catalyst. For this purpose, synthetic zeolite BEA was used as a matrix. The glucose conversion process with the participation of Na-BEA zeolite allowed the following acids to be obtained: levulinic acid, lactic acid, pyruvic acid and formic acid. The highest yield of levulinic acid was achieved when processed for 1–5 h at 200–250 °C with 0.1 g and 0.6 g of Na-BEA catalyst. We also compare the one-pot heterogeneous process with similar homogeneous process using H2SO4 as catalyst.

Sustainable production of gluconic acid and glucuronic acid via microwave-assisted glucose oxidation over low-cost Cu-biochar catalysts

Gluconic acid and glucuronic acid are produced from biomass-derived glucose over low-cost biochar-supported Cu catalysts in a microwave-enhanced base-free system.

Sustainable Hybrid Route to Renewable Methacrylic Acid via Biomass-Derived Citramalate

The combined chemical technologies of microbial fermentation and thermal catalysis provide a hybrid process for sustainable manufacturing of biorenewable sugar-derived monomers for plastics. In this work, methacrylic acid (MAA), a target molecule for the polymer industry, was produced from biomass-derived glucose through the intermediate molecule, citramalic acid. The biosynthetic pathway engineered in E. coli produced citramalic acid intermediate with a high yield (91% of theoretical maximum) from glucose by overexpressing citramalate synthase, removing downstream degradation enzyme 3-isopropylmalate dehydratase, and optimizing the fermentation medium. Thermal heterogeneous catalysis converted the citramalate intermediate to MAA via decarboxylation and dehydration. A selectivity of ∼71% for the production of MAA and its intermediate α-hydroxybutyric acid was achieved at a temperature of 250 °C and an acidity of 1.0 mol acid/mol citramalate. An alumina catalyst was found to enhance the selectivity to MAA in a single reactor pass from 45.6% in the absence of catalyst to 63.2%. This limited selectivity to MAA was attributed to equilibrium between MAA and α-hydroxybutyric acid, but the overall process selectivity to MAA was shown to be higher upon separation and recycle of reaction intermediates. The highest overall glucose-to-MMA yield was 0.65 mol MAA per mole of glucose. A process flow diagram was proposed of the hybrid route for the conversion of glucose to the final end product, methacrylic acid, for poly(methyl methacrylate) (PMMA).

Cooperative Brønsted-Lewis acid sites created by phosphotungstic acid encapsulated metal–organic frameworks for selective glucose conversion to 5-hydroxymethylfurfural

Production of 5-hydroxymethylfurfural (HMF) from biomass-derived glucose has great potential for synthesis of renewable fuels and chemicals. Selective glucose conversion to 5-hydroxymethylfurfural requires a balance between Lewis and Brønsted acids for the cascade of glucose isomerization followed by fructose dehydration. A dual Brønsted-Lewis acid, phosphotungstic acid encapsulated MIL-101(Al)–NH2 metal–organic frameworks (MOFs) was developed to catalyze the glucose dehydration reaction. The encapsulated catalysts had a high HMF selectivity of 58% at 44% glucose conversion at 120 °C in [C4C1im]Cl. Phosphotungstic acid was uniformly dispersed in the MOF pores, which provided both Brønsted and Lewis acid sites for this cascade reaction. The Brønsted acidic phosphotungstic acid-encapsulated MOF catalyst was stable and recyclable at least four times. These findings explain the effect of phosphotungstic acid location for maximizing the HMF selectivity and suggest a new approach for the design of bifunctional solid acid catalysts for selective HMF production from glucose. Moreover, the tunability of the acid properties of the encapsulated MOF catalysts provides opportunities for other biomass transformations.

Thermal Catalytic Conversion of Biomass-Derived Glucose to Fine Chemicals

The energy crisis is a major challenge for the 21st century due to fossil fuel depletion. Biomass, the waste material from plants or animals containing renewable and abundant carbon resources, is considered as an ideal alternative for fossil fuels. Glucose, as a building unit of cellulose, is the most widely used monosaccharide that has wide applications ranging from pharmaceuticals and food industries. The conversion of biomass-derived glucose has become a major and multidisciplinary field of research. Various catalytic transformation processes have been used in the thermochemical conversion of glucose. Numerous nanocatalysts have been developed to selectively convert biomass-derived glucose into fine chemicals. This review mainly summarizes the recent achievements of developing catalytic systems for glucose conversion into high-value chemicals. The catalyst structure–activity relationships and underlying reaction mechanisms are also discussed.

New insights on the selective electroconversion of the cellulosic biomass-derived glucose at PtAu nanocatalysts in an anion exchange membrane fuel cell

Cellulosic biomass, which is basically a polymer of glucose, is the most abundant organic polymer on earth and there is significant interest in the development of advanced materials for its valorization through the waste-to-energy and water-to-chemical scenarios. Hence, a precise investigation of the monomer (glucose) electrooxidation in electrochemical reactors is a key starting point to tackle the whole cellulose and ultimately the entire biomass. To this end, we report herein new insights about the operation of a cogeneration direct alkaline glucose fuel cell (which includes an anion exchange membrane) that simultaneously produces electricity and mainly gluconate as the reaction product. The AuPt nanocatalysts of 3–5 nm particle size finely dispersed onto reduced graphene oxide (rGO) at a 20 wt% metal loading are obtained from an organic surfactant-free method, so-called the bromide anion exchange (BAE). Specifically, the electroanalytical investigation carried out with high-performance liquid ionic chromatography (HPLIC) and liquid chromatography coupled to mass spectrometry (LC-MS) demonstrate no carbon–carbon bond cleavage occurs, which represents an advance towards a CO2-free biomass valorization process. The comparison of the results commonly obtained in a three-electrode half-cell with those in an anion exchange membrane fuel cell shows that the trends in selectivity are the same. The fuel cell operation produces gluconate via a two-electron transfer process at 90% selectivity and 65% Faradaic efficiency. In addition to gluconate, glucuronate is also observed; both compounds are high value-added chemicals. This work contributes towards the engineering of novel electrocatalytic interfaces for the valorization of the surplus biomass into energy and chemicals.

Natural mineral bentonite as catalyst for efficient isomerization of biomass-derived glucose to fructose in water.

The development of inexpensive and efficient heterogeneous catalyst for the conversion of biomass including food and winery processing waste to value-added products is crucial in biorefinery. Glucose could be obtained via the hydrolysis of waste cellulose or starch-rich material, and the isomerization of glucose to fructose using either Lewis acid or Brønsted base catalysts is an important route in biorefinery. As a natural clay mineral, bentonite (Bt) is widely used as adsorption material and catalyst support, but how its intrinsic acid-base properties can impact the biomass conversion chemistry is still rarely reported. In this study, we investigated the influence of the textural and acid-base properties of Bt on the glucose isomerization reaction. The reaction kinetics and mechanism, and the effect of Al3+-exchange were explored. The results showed that the activation energy of Bt-catalyzed glucose conversion was 59.0kJmol-1, and the in-situ Fourier transform infrared spectrometer (FT-IR) characterization proved that Brønsted base was responsible for the isomerization. The highest fructose yield of 39.2% with 86.3% selectivity could be obtained at 110°C for 60min in water. Alkaline rinse and calcination can recover most of the catalytic activity of the spent catalyst.

Efficient Catalysts for the Green Synthesis of Adipic Acid from Biomass.

Green synthesis of adipic acid from renewable biomass is a very attractive goal of sustainable chemistry. Herein, we report efficient catalysts for a two-step transformation of cellulose-derived glucose into adipic acid via glucaric acid. Carbon nanotube-supported platinum nanoparticles are found to work efficiently for the oxidation of glucose to glucaric acid. An activated carbon-supported bifunctional catalyst composed of rhenium oxide and palladium is discovered to be powerful for the removal of four hydroxyl groups in glucaric acid, affording adipic acid with a 99 % yield. Rhenium oxide functions for the deoxygenation but is less efficient for four hydroxyl group removal. The co-presence of palladium not only catalyzes the hydrogenation of olefin intermediates but also synergistically facilitates the deoxygenation. This work presents a green route for adipic acid synthesis and offers a bifunctional-catalysis strategy for efficient deoxygenation.

Catalytic Formation of Lactic and Levulinic Acids from Biomass Derived Monosaccarides through Sn-Beta Formed by Impregnation

In the present study, the use of Sn-Beta zeolite to facilitate the conversion of lignocellulosic biomass-derived glucose and xylose into lactic and levulinic acid was explored. The reactions were carried out in a batch reactor using water as the solvent. Water is the preferred solvent over methanol as it reduces downstream product acid recovery and purification complexity. Optimization experiments were performed for reaction temperature and residence time. Under optimized reaction conditions, the Sn-Beta facilitated reaction of a pure sugar solution resulted in lactic acid yields of 13 and 19 wt% of inlet carbon of glucose and xylose, respectively, plus levulinic acid yields of 18 and 0.8 wt%, respectively. When actual biomass-derived sugar solutions were tested, the yields of lactic acid were significantly higher than those from the optimized model solution experiments with lactic acid yields of 34 wt%. These biomass-derived sugar solutions contained residual levels of CaSO4 from the neutralization step of the hydrolysis process. Further experiments were performed to examine the potential effects from CaSO4 contributing to this increase. It was found that the sulfate ions increased the Brønsted basicity and the calcium increased the Lewis acidity of the reaction solution, and that the combination of both effects increased the conversion of the original sugars into lactic acid. These effects were verified by testing other organic bases to isolate the Brønsted acid neutralization effect and the Lewis acid enhancement effect. The addition of CaSO4 resulted in attractive lactic acid yields, 68 wt% and 50 wt% of inlet carbon from pure glucose and xylose solutions, respectively. Increasing the actual corn stover and forage sorghum derived sugars concentration (in water) allowed lactic acids yields of greater than 60 wt% to be achieved. When the optimized Sn-Beta reaction system was applied to corn stover and forage sorghum mixtures, it was found that the ratio of lactic-to-levulinic acid generated was inversely dependent upon the glucose-to-xylose ratio in the recovered sugar mixture.

Effective selectivity conversion of glucose to furan chemicals in the aqueous deep eutectic solvent

This work demonstrated a smart route of biomass-derived glucose conversion in a biphasic aqueous deep eutectic solvent (DES), which was formed by glucose, ChCl, water, and co-solvent EtAc. Four kinds of value-added furan chemicals, including 5-Hydroxymethylfurfural (HMF), 5-(Acetyloxy) methyl furfural (AMF), 5-Chloromethylfurfural (CMF) and 5-Ethoxymethylfurfural (EMF) were successfully synthesized through a single-step reaction by monitoring the reaction conditions. High yield to 73.2% furan products, including 52.9% of HMF and 17.5% of AMF was obtained from a high concentration of glucose under mild conditions. Moreover, the produced furan mixture could further be converted into other useful chemicals, 2,5-furan dicarboxylic acid (FDCA) and 2,5-dimethyl furan (DMF), directly through simple oxidation and hydrogenation methods, respectively. This study suggested a sustainable synthetic pathway from abundant biomass glucose to furan products and value-added chemicals in the presence of completely green material and catalysts, which showed advantages for the industrial application.

Production of 5-hydroxymethylfurfural (HMF) from rice-straw biomass using a HSO3-ZSM-5 zeolite catalyst under assistance of sonication.

This work studied the application of sulfonated ZSM-5 zeolite, a bi-functional catalyst for conversion of biomass-derived glucose to HMF. Glucose hydrolysate was obtained by enzymatic hydrolysis of rice straw, that was pretreated by sodium hydroxide. Glucose hydrolysate was then subjected to a transformation reaction to achieve HMF using HSO3–ZSM-5 zeolite under the assistance of sonication. The reaction conditions including solvent, temperature, catalyst dosage and reaction time were studied. Suitable conditions, which gave the highest yield of HMF of 54.1% have been found. The HSO3–ZSM-5 zeolite presented a high catalytic efficiency for conversion of glucose to HMF, an important and useful intermediate in the chemical industry.

Simultaneous upgrading of biomass-derived sugars to HMF/furfural via enzymatically isomerized ketose intermediates

BackgroundRecently, exploring fermentative or chemical pathways that convert biomass-derived sugars to fuels/chemicals has attracted a lot of interest from many researchers. We are investigating a hydrocarbon pathway from mixed sugars via 5-hydroxymethyl furfural (HMF) and furfural intermediates. To achieve this goal, we must first convert glucose and xylose to HMF and furfural in favorable yields. Current processes to produce HMF/furfural generally involve the use of acid catalysts in biphasic systems or solvents such as ionic liquids. However, the yield from transforming glucose to HMF is lower than the yield of furfural from xylose.ResultsIn this study, we present an efficient chemical pathway simultaneously transforming glucose and xylose to HMF and furfural via ketose intermediates, i.e., fructose and xylulose, which were generated from glucose and xylose via enzymatic isomerization. In the enzymatic isomerization, by adding sodium borate to complex with the ketoses, xylose conversion reached equilibrium after 2 h with a conversion of 91% and glucose conversion reached 84% after 4 h. By enzymatically isomerizing the aldoses to ketoses, the following dehydration reactions to HMF and furfural could be performed at low process temperatures (i.e., 110–120 °C) minimizing the side reactions of the sugars and limiting the degradation of furfurals to humins and carboxylic acids. At 120 °C, pH 0.5, and 15 min reaction time, mixed ketose sugars were converted to HMF and furfural in yields of 77% and 96%, respectively (based on starting aldose concentrations).ConclusionTaken together, our results demonstrate that this combined biological and chemical process could be an effective pathway to simultaneously convert biomass-derived glucose and xylose to HMF and furfural, for use as intermediates in the production of hydrocarbons.