Biomass-derived Platform Chemicals Research Articles

5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals.

5-Hydroxymethylfurfural (5-HMF) is a biomass-derived platform chemical, which can be produced from carbohydrates. In the past decades, 5- HMF has received tremendous attention because of its wide applications in the production of various value-added chemicals, materials and biofuels. The manufacture and the catalytic conversion of 5-HMF to simple industrially-important bulk chemicals have been well reviewed. However, employing 5-HMF as a building block in organic synthesis has never been summarized exclusively, despite the rapid development in this area. The aim of this review is to bring a fresh perspective on the use of 5-HMF in organic synthesis, to the exclusion of already well documented conversion of 5-HMF towards relatively simple molecules such as 2,5-furandicarboxylic acid, 2,5-dimethylfuran and so on notably used as monomers or biofuels. As it has been shown throughout this review, 5-HMF has been the object of numerous studies on its use in fine chemical synthesis. Thanks to the presence of different functional groups on this platform chemical, it proved to be an excellent starting material for the preparation of various fine chemicals. The use of this C-6 synthon in novel synthetic routes is appealing, as it allows the incorporation of renewable carbonsources into the final targets.

Selective Catalysis for Room-Temperature Hydrogenation of Biomass-Derived Compounds over Supported NiPd Catalysts in Water

Utilizing biomass-derived furan-based platform chemicals for the production of a wide range of value-added components for application as fuels/fuel blenders and other fine chemicals is gaining much attention. Here, we demonstrated an efficient room-temperature selective hydrogenation of furan-based long chain aldol compounds over supported NiPd/SiO2, NiPd/RHA (RHA is rice-husk ash), and NiPd/Z4A (Z4A is zeolite 4A) catalysts in water. A wide range of furan-based compounds, such as 1,5-bis(furan-2-yl)penta-1,4-dien-3-one (1), 4-(furan-2-yl)but-3-en-2-one (3), 1,3-bis(furan-2-yl)prop-2-en-1-one (4), 1-(furan-2-yl)-3-(5-methylfuran-2-yl)prop-2-en-1-one (5), and 3-(furan-2-ylmethylene)pentane-2,4-dione (6), were conveniently hydrogenated to the corresponding saturated ketone products using the present protocol. Our findings inferred that the studied supported NiPd catalysts selectively promoted the hydrogenation of the C═C bond over the C═O bond to yield the corresponding saturated ketone products. The observed tuned catalytic properties can be attributed to the crucial role of the support in controlling the substrate-to-surface interactions, presumably, by disfavoring the interaction of polar carbonyl functional groups with the catalyst surface and, hence, facilitating the hydrogenation of C═C over C═O bonds. Moreover, the support RHA facilitated the high dispersion of NiPd nanoparticles (∼4 nm) for the NiPd/RHA catalyst. Hence, the NiPd/RHA catalyst displayed high stability under the catalytic reaction conditions and was reused for six consecutive catalytic runs without any significant loss in the catalytic activity.

Renewable natural resources as green alternative substrates to obtain bio-based non-isocyanate polyurethanes-review

Commercially available polyurethanes are synthesized by the polyaddition of diisocyanates with polyols and low molecular weight chain extenders. A new approach to polyurethanes synthesis is realized via non-isocyanate routes. Negative impacts of petroleum-based chemicals on the environment and human health as well as gradual reduction of fuel-based resources, which leads to an increase in their prices, are an incentive to looking for bio-based components derived from renewable resources for the polyurethanes synthesis. The purpose of the presented review is a critical summary of the possibilities of using renewable natural resources as green intermediates to obtain non-isocyanate polyurethanes by polyaddition of bis(cyclic carbonate)s and di- or polyamines. The possibility of using carbon dioxide, plant oils, fatty acids and biomass-derived platform chemicals in non-isocyanate polyurethane synthesis is exhaustively commented.

Production of lactic acid from cellulose using solid catalyst

Lactic acid (LA), one of the important biomass derived platform chemicals, has been used in food and chemical industries, especially in biodegradable polymer as polylactic acid (PLA). The aim of this work is to study the one-pot production of LA from cellulose by using different solid catalysts. The reaction was conducted in a high pressure batch reactor and the catalyst used in this study were ZrO2 and Al2O3. The reaction was carried out at temperature of 200oC for 6 hr. and under nitrogen pressure of 1 MP. It was found that the production yield of LA were 8.02% and 6.63%, when the ZrO2 and Al2O3 catalysts were used respectively. The result indicated that the ZrO2 may effect on the LA production because of the acid and base sites of the ZrO2. Therefore, the reaction pathways for conversion of cellulose into lactic acid have been investigated, and developed the new conditions to achieve the higher yield.

Chemical Transformations of Biomass-Derived C6-Furanic Platform Chemicals for Sustainable Energy Research, Materials Science, and Synthetic Building Blocks

Recent advances in the area of biomass-derived C6-furanic platform chemicals for sustainable biomass processing are analyzed focusing on chemical reactions important for development of practical applications and materials science. Among the chemical processes currently being studied, tuning the amount of oxygen-containing functional groups remains the most active research direction. Production of efficient fuels requires the removal of oxygen atoms (reduction reactions), whereas utilization of biomass-derived furanic derivatives in material science points out the importance of oxidation in order to form dicarboxylic derivatives. Stimulated by this driving force, oxidation and reduction of 5-(hydroxymethyl)furfural (HMF) are nowadays massively studied. Moreover, these fundamental transformations are often used as model reactions to test new catalysts, and HMF transformations guide the development of new catalytic systems. From the viewpoint of organic synthesis, highly diverse chemical reactivity is explor...

Production of 5-HMF from Cellulosic Biomass: Experimental Results and Integrated Process Simulation

5-Hydroxymethylfurfural (5-HMF) is one of the most promising biomass derived platform chemicals. It can be synthesized from biomass carbohydrates, mainly glucose and fructose, via dehydration under acidic conditions. The reaction may be performed either in water, ionic liquids or organic solvents, in particular polar aprotic solvents. In this work, the process modelling of a two-step synthesis of 5-HMF from biomass is presented. Starting from hemicellulose-free biomass, the first step includes the hydrolysis of cellulose towards glucose in the presence of H2SO4 as catalyst, while in a second step glucose is dehydrated to 5-HMF with the aid of Sn20/γ-Αl2O3 catalyst. Hydrolysis is performed in aqueous medium, while dehydration of glucose is taking place in a DMSO/H2O mixture. The overall production of 5-HMF is modelled via the chemical process optimization software ASPEN PLUS™. The optimized process is scaled up at an industrial scale where the heat integration, mass and energy balance calculations are performed.

Heuristics To Guide the Development of Sustainable, Biomass-Derived, Platform Chemical Derivatives

Hundreds of catalytic routes to upgrade biomass-derived platform chemicals have been proposed. In this study, we developed process selection and development heuristics for these catalytic transformations from techno-economic analysis of catalytically upgrading furfural (a potential platform chemical) to eight derivatives that vary in chemical functionality and process complexity. These heuristics included simple cost equations based on catalyst performance as well as process complexity to predict the minimum selling price of platform chemical derivatives. Additionally, design rules were developed to guide the development of catalytic technologies for upgrading platform chemicals. The conversion of platform chemicals to hydrocarbons must be avoided. For commercial relevance, attaining catalyst yield of 60% and weight hourly space velocity of at least on the order of 0.1 h–1 are necessary. Precious metal catalysts, such as Pt, cannot be used if the desired platform chemical derivative is priced below 1.00 (...

DOSY Plus Selective TOCSY: An Efficient NMR Combination for Analyzing Hydrogenation/Hydrogenolysis Mixtures of Biomass-Derived Platform Compounds

Analyzing the mixtures obtained from hydrogenation or hydrogenolysis reactions of biomass-derived platform chemicals is challenging work. With the development and improvement of NMR techniques, the NMR spectrometer proves to be an alternative and highly efficient piece of equipment for the rapid analysis of complex mixtures without the need for tedious purification. Herein, diffusion-ordered spectroscopy (DOSY) is applied in analyzing four model mixtures, which consist of the reactants and products from hydrogenation/hydrogenolysis reactions of biomass-derived platform chemicals. The results show that the DOSY technique can pseudoseparate most components in the model mixtures. The 1D selective gradient TOCSY technique is used as a supporting tool in the cases where the DOSY technique cannot clearly distinguish between the components of the mixtures. This is generally a problem when components in the mixture have very similar diffusion coefficients or severe overlap of peaks. The results show that DOSY and...

Efficient bioconversion of organic wastes to high optical activity of l-lactic acid stimulated by cathode in mixed microbial consortium.

Lactic acid is one of the emerging top biomass derived platform chemicals that can be fermented from organic wastes. This study evaluated the potential of Cathodic Electro-Fermentation (CEF) as a novel approach to enhance the yield of high optical activity (OA) of l-lactic acid from organic wastes using mixed microbial consortium. The fermentation process was stimulated through the cathode applied with-100 mV versus standard hydrogen electrode (SHE), which contributed to 4.73 times higher lactic acid productivity (0.6578 g L-1 h-1) compared to that in the open circuit control (0.1392 g L-1 h-1), and an improved OA of l-lactic acid was also observed (42.3% vs. 3.6% of the open circuit control). The study elucidated that the optimal voltage at-100 mV promoted the conversion of pyruvate to l-lactate by 77.9% compared to the Blank, which triggered the generation of l-lactic acid to occur rapidly even at low concentration of pyruvate. The significant variation of microbial community in family- and genus-level distributions were observed in CEF system. Furthermore, the open-circuit operation test demonstrated that the cathode providing in-situ electron supply was essential to achieve high efficient bioconversion of organic wastes to lactic acid. Our work highlights the feasibility of CEF to steer high value-added fermentation products deriving from organic wastes by the mixed microbial consortium.

Ru-Sn/AC for the Aqueous-Phase Reduction of Succinic Acid to 1,4-Butanediol under Continuous Process Conditions

Succinic acid is a biomass-derived platform chemical that can be catalytically converted in the aqueous phase to 1,4-butanediol (BDO), a prevalent building block used in the polymer and chemical industries. Despite significant interest, limited work has been reported regarding sustained catalyst performance and stability under continuous aqueous-phase process conditions. As such, this work examines Ru-Sn on activated carbon (AC) for the aqueous-phase conversion of succinic acid to BDO under batch and flow reactor conditions. Initially, powder Ru-Sn catalysts were screened to determine the most effective bimetallic ratio and provide a comparison to other monometallic (Pd, Pt, Ru) and bimetallic (Pt-Sn, Pd-Re) catalysts. Batch reactor tests determined that a ∼1:1 metal weight ratio of Ru to Sn was effective for producing BDO in high yields, with complete conversion resulting in 82% molar yield. Characterization of the fresh Ru-Sn catalyst suggests that the sequential loading method results in Ru sites that ...

Mechanistic Insight into the Electrocatalytic Hydrogenation and Electroreduction of Furfural

Electrochemical reduction of biomass-derived platform chemicals is an emerging route for biofuels and chemicals production, where renewable electricity drives reactions on electrodes without the need for external hydrogen supply.1-3 However, the mechanisms governing electrochemical reduction of biomass-derived furanic compounds and its competition with hydrogen evolution reaction (HER) remain unclear. In this talk, we investigate the electrochemical reduction of furfural on copper electrodes for the production of 2-methylfuran (an important potential biofuel additive), furfuryl alcohol (a valuable chemical building block), and dimerization products. Through novel electrochemical techniques, we distinguish between two mechanisms – electrocatalytic hydrogenation (ECH) and outer-sphere electroreduction (ER). Understanding of the underlying mechanisms enables us to tune product selectivity and the competition between ECH, ER, and HER by varying reaction conditions including cathode potential, initial furfural concentration and electrolyte pH. Cyclic voltammetry and bulk electrolysis results clarify the reaction pathways of 2-methylfuran and furfuryl alcohol formation under these conditions. We demonstrate that electrochemical reduction is a promising route for selective furfural conversion and highlight the importance of the underlying mechanisms. These findings can be applied to related biomass-derived platform chemicals including 5-(hydroxymethyl)furfural and other carbonyl-containing compounds.

A new approach of probe sonication assisted ionic liquid conversion of glucose, cellulose and biomass into 5-hydroxymethylfurfural

5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to β-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.

Production of Levoglucosenone and Dihydrolevoglucosenone by Catalytic Reforming of Volatiles from Cellulose Pyrolysis Using Supported Ionic Liquid Phase

This paper presents a novel method for continuous production of a biomass-derived platform chemical, levoglucosenone (LGO), from cellulose without its pretreatment or use of solvent. First, cellulose is pyrolyzed, and then the volatiles are reformed over a catalyst consisting of a type of ionic liquid supported over porous char. The ionic liquid, having a moderate hydrogen-bond basicity, performs well in the dehydrative conversion of levoglucosan (LGA) and anhydrosugar oligomers in the volatiles to LGO at 275 °C. The catalytic reforming to LGO is highly selective, and consequently, the yield of LGO is determined mainly by the pyrolysis conditions that produce the LGO precursors. The highest LGO yield we obtained was 31.6% on a cellulose carbon basis (24.6 wt %) with fast pyrolysis that produced more precursors than the slow one. Furthermore, the reaction system is applicable to the production of dihydrolevoglucosenone (DLGO), a promising biobased alternative to dipolar aprotic solvents. Addition of hydrog...

Direct catalytic conversion of brown seaweed-derived alginic acid to furfural using 12-tungstophosphoric acid catalyst in tetrahydrofuran/water co-solvent

Furfural, a biomass-derived platform chemical, was produced by acid-catalyzed reaction of alginic acid extracted from brown seaweed. Three acid catalysts, H2SO4, Amberlyst15 and 12-tungstophosphoric acid (H3PW12O40), were compared to evaluate their catalytic performance for the alginic acid conversion. The H3PW12O40 catalyst showed the highest catalytic activity, yielding the maximum furfural yield (33.8%) at 180°C for 30min in tetrahydrofuran/water co-solvent. Higher reaction temperature promoted the conversion of alginic acid to furfural, but the transformation of furfural to humin was also accelerated. To our knowledge, this is the highest furfural yield among studies about the direct catalytic conversion of alginic acid. Furthermore, products distribution with time-on-stream was investigated in detail, which led us to propose a reaction pathway.

Electrocatalytic Upgrading of Furfural to Produce Biofuels and Fine Chemicals: Synergistic Effects Between Cu Electrocatalysts and Electrolytes

Furfural (FF) is an important biomass-derived platform chemical, which offers a rich source of derivatives that can be used as promising industrial chemicals and biofuel components such as furfuryl alcohol (FA) and 2-methyl furan (MF)1,2. For this reason, chemical hydrogenation and hydrogenolysis (CH) of FF has been studied to obtain target products FA and MF extensively. Selective conversion has been mainly obtained over Cu-containing heterogeneous catalysts depending upon reaction conditions such as temperature, pressure, and catalyst loading and partial pressures of H2 in vapor phase3-5. Frequently, the reduction conditions require moderate pressures of hydrogen and moderate reaction temperatures (200 – 300oC) 3-5. As an alternative to CH, electrocatalytic hydrogenation and hydrogenolysis (ECH) allows for furfural reduction without the use of externally supplied hydrogen gas at mild reaction conditions. Rather, the electrolyte and electrochemical process provide the means to reduce FF. Similar to the heterogeneous catalysis work, Cu-based electrocatalysts have shown promise in ECH as well. Cu electrodes resulted in higher selectivities towards MF in acidic electrolytes than other metal electrodes investigated in the literature6. Additionally, Cu has a relatively higher hydrogen overpotential compared to noble metals7, allowing for ECH to occur rather than the competitive hydrogen evolution reaction. Our research has focused on the synergistic effects between Cu electrocatalysts and the electrolytes used. The pH, anions and cations used, and the mixtures of organic and aqueous solutions used all have a significant impact on the selectivity of ECH between MF and FF. For example, the selectivity of MF was 10 times higher than that of FA in 0.5M H2SO4 in 1:4 (vol) acetonitrile:water, but only FA was produced using the same Cu electrode in 0.2M NH4Cl in 1:4 (vol) acetonitrile:water. The relationships between electrolyte and product selectivity along with the impact of Cu catalyst morphology will be reported.

Design of highly ordered mesoporous Nb2O5-based hybrid catalysts bifunctionalized by the Keggin-type heteropoly acid and phenyl-bridged organosilica moieties for the synthesis of methyl levulinate

Highly ordered mesoporous Nb2O5-based hybrid catalysts bifunctionalized by the Keggin-type heteropoly acid and phenyl-bridged organosilica moieties (PW12/Nb2O5-Si(Ph)Si) were prepared by a P123-directed one step sol–gel route combined with hydrothermal treatment. The main steps included co-condensation of bridged silsesquioxane with NbCl5 in the presence of H3PW12O40 and carefully adjusting Si-to-Nb molar ratio in the initial gel mixture. The pore morphologies and porosity properties, Brønsted and Lewis acid nature of the hybrid catalysts as well as the structure integrity of the starting H3PW12O40 and bridging phenyl moieties in the hybrid catalysts were well characterized. The heterogeneous acid catalytic activity of the PW12/Nb2O5-Si(Ph)Si was evaluated in esterification of levulinic acid (one of the important biomass-derived platform chemicals) with methanol to produce methyl levulinate. The obtained excellent esterification activity was explained by the combination of advantages of strong Brønsted and moderate Lewis acidity, excellent porosity properties and hydrophobic surface of the hybrid catalysts. Additionally, the catalysts can be reused for three times without significant activity loss.

Evaluating the toxicity of biomass derived platform chemicals

Furans and their derivatives are well-known chemical building blocks common in plant biomass, and are abundantly used in food, medicines and industrial processes.

Synthesis of HIV-1 capsid protein assembly inhibitor (CAP-1) and its analogues based on a biomass approach.

A biomass-derived platform chemical was utilized to access a demanded pharmaceutical substance with anti-HIV activity (HIV, human immunodeficiency virus) and a variety of structural analogues. Step economy in the synthesis of the drug core (single stage from cellulose) is studied including flexible variability of four structural units. The first synthesis and X-ray structure of the inhibitor of HIV-1 capsid protein assembly (CAP-1) is described.

Experimental and Kinetic Modeling Studies on the Sulfuric Acid Catalyzed Conversion of d-Fructose to 5-Hydroxymethylfurfural and Levulinic Acid in Water

Levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) have been identified as promising biomass-derived platform chemicals. A kinetic study on the conversion of d-fructose to HMF and LA in water using sulfuric acid as the catalyst has been performed in batch setups. The experiments were carried out in a temperature window of 140–180 °C, using sulfuric acid as the catalyst (0.005–1 M) and an initial d-fructose concentration between 0.1 and 1 M. A kinetic model for the conversion of d-fructose to HMF and the subsequent reaction of HMF to LA was developed including the kinetics for the formation of solid byproducts (humins) using a power-law approach. According to the model, the maximum attainable HMF yield in the experimental window is 56 mol % (Cfruc = 0.1 M; Cacid = 0.005 M; 166 °C), which is close to the highest experimental value within the range (53 mol %) and considerably higher than that reported for d-glucose. The highest modeled LA yield was 70 mol % (Cfruc = 0.1 M; Cacid = 1 M; 140 °C), close to t...

Recent Advances in the Catalytic Synthesis of 2,5-Furandicarboxylic Acid and Its Derivatives

Catalytic synthesis of value-added chemicals from renewable biomass or biomass-derived platform chemicals is an important way to reduce current dependence on fossil-fuel resources. In recent years, 2,5-furandicarboxylic acid (FDCA) has received significant attention due to its wide application in many fields, particularly as a substitute of petrochemical-derived terephthalic acid in the synthesis of useful polymers. Therefore, much effort has been devoted to the catalytic synthesis of FDCA. In this critical review, we will provide an overview of concise and up-to-date methods for the synthesis of FDCA from HMF oxidation or directly from carbohydrates by one-pot reaction, giving special attention to catalytic systems, mechanistic insight, reaction pathway, and catalyst stability. In addition, the one-pot oxidative conversion of carbohydrates into FDCA and the one-pot synthesis of FDCA derivatives are also discussed. It is anticipated that the chemistry detailed in this review will guide researchers to deve...