Biomass-derived Platform Chemicals Research Articles

Furfural separation from aqueous solution by pervaporation membrane mixed with metal organic framework MIL-53(Al) synthesized via high efficiency solvent-controlled microwave

• MIL-53(Al) particles (MAPs)/PEBA mixed matrix PV membranes were fabricated. • Anisotropic morphology and particle size of MAPs were precisely manipulated. • Incorporating MAPs facilely addressed trade-off effect in PV membrane. • MAPs reduced the permeation energy barrier for furfural, but not for water. • The MMMs had high performance and long-term stability in simulated hydrolysate. Furfural is a typical biomass-derived platform chemical. Conventional processes for furfural production are uneconomical and energy-intensive because only about 3–6 wt% of furfural in the hydrolysate needs to be separated. In this study, a series of mixed matrix membranes (MMMs) were prepared by incorporating MIL-53(Al) particles (MAPs) into poly (ether-block-amide) (PEBA 2533) matrix for pervaporation separation of furfural from aqueous solutions. The MAPs with anisotropic morphology and tunable particle size were precisely synthesized by a high-efficiency solvent-controlled microwave synthetic strategy. Effects of MAPs on the microstructures, physicochemical properties of MAPs/PEBA MMMs were investigated in detail through SEM, EDS, XRD, FTIR, TGA, N 2 adsorption and contact angle measurements. The experimental results suggested that compared with the PEBA control membrane, the addition of MAPs notably reduced the permeation energy barrier for furfural, but not for water. The coin-like MAPs-16.7 filled MMMs presented the optimal separation performance, which exceeded other furfural-permselective membranes. Impressively, a high total flux of 3800 g∙m −2 ∙h −1 and an adequate furfural/water separation factor of 50.2 was achieved in PV separation of 1 wt% furfural aqueous solution at 80 °C, which could substantially reduce capital investment and equipment footprint. Furthermore, a continuous testing was operated for 200 h in ternary furfural/acetic acid/water simulated hydrolysate, highlighting the long-term membrane stability in realistic applications. High performance and long-term stability made MAPs/PEBA MMMs potential candidates for industrial furfural production.

A non-catalytic process to produce levulinic acid from the flesh fruits of trembesi (Samanea saman) using a subcritical water

Levulinic acid (LA) has been identified as a promising green, biomass-derived platform chemical. A non-catalytic method to produce LA from the flesh fruits of trembesi (Samanea saman) using subcritical water has been performed. Effect of reaction time and operating pressure under CO2 atmosphere on the conversion of glucose and yield of LA has been investigated. The conversion of glucose was found to be affected by the reaction time rather than operating pressure. The longer reaction time from 30 to 480 min. increased the conversion of glucose from 87.72% ± 1.57% to 98.74 ± 1.76% or increased by 12.56% at 200 °C, 4 MPa and ratio of flesh fruit and water of 1/8 (g/ml). Increasing the operating pressure from 4 MPa to 8 MPa, only increased the conversion of glucose by 4.67%. The yield of LA was found to be affected by the reaction time and operating pressure. The yield of LA was increased by 61.88 % by increasing reaction time from 30 to 240 min, while extended further reaction time to 480 min. the reduced yield of LA by 24.05 %. The highest yield of LA (22.28 ± 0.04 %) can be achieved in 240 min at 200 °C and 8 MPa. The result showed that LA could be obtained by a green method.

Recent Progress in 5-Hydroxymethylfurfural Catalytic Oxidation to 2,5-Furandicarboxylic Acid

Biomass has attracted much attention because of its clean and renewable characteristics. The conversion of biomass into various fine chemicals and high value-added fuels is one of the important ways to solve the energy shortage and environmental pollution. 2,5-furan dicarboxylic acid (FDCA), a kind of important and promising new bio-based monomer, has attracted the attention of many researchers due to its wide applications in different industries. Therefore, many efforts have been made over various metal catalysts for FDCA production from this biomass-derived platform chemical, 5hydroxymethylfurfural (HMF). In this review, we introduced the reaction pathways of the aerobic oxidation of HMF to FDCA and summarized the recent progress of different catalysts and catalysis for HMF aerobic oxidation. Catalytic performance and reaction pathways are discussed in detail. Finally, conclusions and the remaining challenges are proposed and further prospects are presented in view of the technical aspects.

Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by Visible Light-Driven Photocatalysis over In Situ Substrate-Sensitized Titania.

Solar energy‐driven processes for biomass valorization are priority for the growing industrialized society. To address this challenge, efficient visible light‐active photocatalyst for the selective oxidation of biomass‐derived platform chemical is highly desirable. Herein, selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) was achieved by visible light‐driven photocatalysis over titania. Pristine titania is photocatalytically inactive under visible light, so an unconventional approach was employed for the visible light (λ=515 nm) sensitization of titania via a formation of a visible light‐absorbing complex of HMF (substrate) on the titania surface. Surface‐complexation of HMF on titania mediated ligand‐to‐metal charge transfer (LMCT) under visible light, which efficiently catalyzed the oxidation of HMF to DFF. A high DFF selectivity of 87 % was achieved with 59 % HMF conversion after 4 h of illumination. The apparent quantum yield obtained for DFF production was calculated to be 6.3 %. It was proposed that the dissociative interaction of hydroxyl groups of HMF and the titania surface is responsible for the surface‐complex formation. When the hydroxyl groups of titania were modified via surface‐fluorination or calcination the oxidation of HMF was inhibited under visible light, signifying that hydroxyl groups are decisive for photocatalytic activity.

Nanoengineered Electrodes for Biomass-Derived 5-Hydroxymethylfurfural Electrocatalytic Oxidation to 2,5-Furandicarboxylic Acid

Over the last decades, there has been significant progress toward the development of advanced electrochemical processes in the fields of energy production and storage, surface modification of materials and environmental remediation. Within the context of biomass valorization and biorefineries, the electrochemical oxidation of 5-hydroxymethylfurfural (HMF), one of the top biomass-derived platform chemicals, to 2,5-furandicarboxylic acid (FDCA), a valuable monomer and building block of polyethylene furanoate (PEF), has emerged as a promising sustainable alternative to the chemo-catalytic synthesis paths. An additional asset of the electrochemical route is the simultaneous production of H2. The rational design of efficient nanocatalysts and nanoengineered anodes requiring lower oxidation potential is anticipated to lead to HMF electrocatalytic oxidation at even smaller applied voltage. Additionally, the utilization of heterogeneous photocatalysis combined with advantages offered by photoelectrodes capable to utilize directly the solar light, known as photoelectrochemical (PEC) catalysis, can limit the application of external voltage. This review covers all recent developments related to electrochemical oxidation of HMF to FDCA, with emphasis on the nanoengineered anodes and their structural, morphological and chemical features, as well as with regard to the associated reaction mechanisms. The potential of solar-driven photoelectrochemical oxidation methods and continuous flow electrochemical oxidation is also discussed.

Taming the butterfly effect: modulating catalyst nanostructures for better selectivity control of the catalytic hydrogenation of biomass-derived furan platform chemicals

This minireview highlights versatile routes for catalyst nanostructure modulation for better hydrogenation selectivity control of typical biomass-derived furan platform chemicals to tame the butterfly effect on the catalytic selectivity.

Development of a continuous-flow tubular reactor for synthesis of 5-hydroxymethylfurfural from fructose using heterogeneous solid acid catalysts in biphasic reaction medium

5-Hydroxymethylfurfural (5-HMF) is an important biomass-derived platform chemical used to produce polymers, biofuels, and other valuable industrial chemicals.

Metal phosphate catalysts to upgrade lignocellulose biomass into value-added chemicals and biofuels

This review presents an overview of the transformation of biomass-derived platform chemicals into value-added chemicals and biofuels using metal phosphate-based heterogeneous catalysts.

Sustainable production of 5-hydroxymethyl furfural from glucose for process integration with high fructose corn syrup infrastructure

Development of an economic and sustainable process for production of a biomass-derived platform chemicals, 5-hydroxymethyl furfural (HMF), utilizing the infrastructure for production of high fructose corn syrup (HFCS).

Modulation of Ru and Cu nanoparticle contents over CuAlPO-5 for synergistic enhancement in the selective reduction and oxidation of biomass-derived furan based alcohols and carbonyls

Cu–Ru NP decorated CuAlPO-5 catalysts with low contents of Ru exhibit excellent activity and selectivity in the reduction and the oxidation of biomass-derived platform chemicals.

Understanding the geometric and electronic factors of PtNi bimetallic surfaces for efficient and selective catalytic hydrogenation of biomass-derived oxygenates

Selective and efficient upgrading of furfural over controllable PtNi bimetallic catalyst under mild conditions. Ni-base catalysts are promising candidate for the hydrogenation of furfural (FAL) to high-value chemicals. However, slow intermediate desorption and low selectivity limit its implementation. Identifying the catalytic performance of each active sites is vital to design hydrogenation catalyst, and tuning the geometrical sites at molecule level in PtNi could lead to the modification of electronic structure, and thus the selectity for the hydrogenation of FAL was modulated. Herein, PtNi hollow nanoframes (PtNi HNFs) with three dimensional (3D) molecular accessibility were synthesized, EDX results suggested that Ni was evenly distributed inside of the hollow nanoframes, whereas Pt was relatively concentrated at the edges. DFT calculation demonstrated that PtNi significant decrease the desorption energy of the intermediates. This strategy could not only enhance the desorption of intermediates to improve the catalytic performance, but also transfer the adsorption mode of FAL on catalyst surface to selective hydrogenation of FAL to FOL or THFA. The PtNi HNFs catalyst afforded excellent catalytic performance for selective hydrogenation of a broad range of biomass-derived platform chemicals under mild conditions, especially of FAL to furfuryl alcohol (FOL), in quantitative FOL yields (99%) with a high TOF of 2.56 h −1 . It is found that the superior performance of PtNi HNFs is attributed to its 3D hierarchical structure and synergistic electronic effects between Pt and Ni. Besides, the kinetic study demonstrated that the activation energy for hydrogenation of FAL was as low as 54.95 kJ mol −1 .

Catalytic C−H Functionalization of Unreactive Furan Cores in Bio‐Derived Platform Chemicals

C-H functionalization is one of the most convenient and powerful tools in the arsenal of modern chemistry, deservedly nominated as the "Holy Grail" of organic synthesis. A frequent disadvantage of this method is the need for harsh reaction conditions to carry out transformations of inert C-H bonds, which limits the possibility of its use for modifying less stable substrates. Biomass-derived furan platform chemicals, which have a relatively unstable aromatic furan core and highly reactive side chain substituents, are extremely promising and valuable organic molecules that are currently widely used in a variety of research and industrial fields. The high sensitivity of furan derivatives to acids, strong oxidants, and high temperatures significantly limits the use of classical methods of C-H functionalization for their modification. New methods of catalytic functionalization of non-reactive furan cores are urgently required to obtain a new generation of materials with controlled properties and potentially bioactive substances.

Zinc-Catalyzed Electrocatalytic Hydrogenation of Furfural at Neutral pH

Electrocatalytic hydrogenation (ECH) of biomass-derived platform chemicals is a sustainable way to produce value added fuels and chemicals as compared to chemo-catalytic hydrogenation pathway [1,2]. In this work, ECH of furfural was carried out to produce furfuryl alcohol (FAL) and 2-methylfuran (MF) which have applications in pharmaceutical, polymer and fuel industries [1-3]. In this work, Zn metal was used as a novel catalyst for the ECH of furfural to study its yield and Faradaic efficiency (FE) for the desired products. The activity of Zn metal was compared to the well-known catalysts such as Cu and Ni. The effect of electrolyte pH was also studied, and it was found to significantly affect FE and product profile. Potentiostatic electrolysis in acidic and basic pH electrolytes suffered from poor product yield and FE, either due to dominant hydrogen evolution reaction (HER) or degradative electrodimerization and polymerization reactions. Electrolysis at neutral pH (pH 6 to 8) exhibited increased yields and FE as compared to acidic and basic pH. We correlate this to optimum proton concentration in neutral electrolytes that would restrict HER in addition to providing a pH atmosphere that would minimize side reactions. At neutral pH, the reaction was more selective towards FAL formation than MF. The best activity of Zn catalyst was obtained with 0.5 M sodium bicarbonate (NaHCO3) electrolyte (pH = 8.4) at -0.7 V/RHE with 77.5 % FE for FAL. The zinc catalyst displayed a total FE of 94 % for the ECH of furfural. At the same reaction conditions, the conversion, yield and FE for ECH with Zn was remarkably higher as compared to Cu and Ni metal electrodes. Zinc oxide precipitates were observed on the wire during electrolysis and were confirmed by EDS. The increased activity of Zn suggests a mechanistic role of adhered ZnO precipitates, possibly enhancing H adsorption and transfer to furfural.

Organic acid catalyzed production of platform chemical 5-hydroxymethylfurfural from fructose: Process comparison and evaluation based on kinetic modeling

Fructose was converted to 5-hydroxymethylfurfural (HMF), an important biomass-derived platform chemical, under mild conditions (100–130 °C) with several organic acids including p-toluene sulfonic (pTSA), oxalic, maleic, malonic and succinic acids as the catalysts. The process kinetics was compared considering fructose dehydration to HMF as the objective reaction and condensation of fructose and HMF to humin and rehydration of HMF as the main side reactions. DMSO was found to be the most effective solvent reaction medium to obtain high fructose conversion and HMF yield. Observed kinetic modeling illustrated that the rehydration and condensation of HMF in DMSO actually could be neglected, especially for the oxalic acid catalyzed system. The determined observed activation energy for fructose conversion to HMF and humin in DMSO medium was 33.75 and 24.94 kJ/mol for pTSA catalyzed system, and 96.51 and 78.39 kJ/mol for oxalic acid-catalyzed system, respectively. HMF yields of 90.2% and 84.1% were obtained for pTSA and oxalic acid catalyzed systems, respectively.

Kinetic Studies on the Impact of Pd Addition to Ru/TiO2 Catalyst: Levulinic Acid to γ-Valerolactone under Ambient Hydrogen Pressure

The conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the most important reactions from biomass-derived platform chemicals to value-added chemicals. In this work, bimetallic PdRu...

Hydrotalcite supported bimetallic (Ni-Cu) catalyst: A smart choice for one-pot conversion of biomass-derived platform chemicals to hydrogenated biofuels

The production of drop-in biofuels 2,5-dimethylfuran (DMF), 2,5-dimethyltetrahydrofuran (DMTHF) from biomass-derived hydrocarbons usually incorporates precious metals as a catalyst. Herein, we developed a bimetallic (Ni-Cu) supported on hydrotalcite (HT) catalyst and applied for catalytic hydrogenation of 5-hydroxymethylfurfural (HMF) and 2,5-bis(hydroxymethyl)furan (BHMF) to 2,5-dimethylfuran (DMF) and other valuable fuel additives at a relatively low temperature (85–130 °C) and pressure (6–20 bar). The effect of other process parameters like reaction time, solvent and catalyst loading on DMF yield was also investigated. Ni-Cu/HT was found to be exceptionally active and selective catalyst for hydro-deoxygenation of HMF to DMF and other high-energy furanics. Ni-Cu/HT was applied under mild reaction condition for hydrogenation of BHMF to DMF and 100% BHMF conversion and 83% DMF yield was obtained at 85 °C and 6 bar hydrogen pressure and 100 mg catalyst loading. 78% over-hydrogenated product (DMTHF) yield was observed at higher catalyst loading (200 mg) at 130 °C. The excellent activity of Ni-Cu/HT catalyst for hydrogenation and deoxygenation is attributed to synergistic-cooperation of Ni and Cu and metal stability owing to hydrotalcite support. Moreover, the acid-base properties of HT also contributed to superior activity of Ni-Cu/HT catalyst by facilitating HMF, BHMF and formic acid adsorption and activation and by promoting hydrogenolysis of C-O ester bond. A detailed characterization of as-synthesized Ni-Cu/HT by TPR, BET, XPS, TEM, HRTEM, FESEM, EDX, powder XRD and FTIR techniques was carried out to examine its structural and morphological features.

Transfer hydrogenation of levulinic acid from glycerol and ethanol using water-soluble iridium N-heterocyclic carbene complexes

The upgrading of biomass derivatives to biofuels and chemicals through transfer hydrogenation (TH) is attractive relative to direct hydrogenation, especially when the hydrogen donors can be sourced renewably. Here we report the first process that uses glycerol, a renewable waste material from biodiesel processing, as a hydrogen donor in the catalytic TH of a biomass-derived platform chemical, levulinic acid, to selectively afford γ-hydroxyvaleric acid (GHV) and lactic acid (LA). GHV can be further converted to γ-valerolactone (GVL), a widely used platform chemical. Levulinic acid can be used directly, without esterification, which is typically needed for transfer hydrogenation. The process is efficiently facilitated by robust iridium N-heterocyclic carbene (NHC) complexes with sulfonate functional groups at low catalyst loading (1–10 ppm), affording quantitative conversion of levulinic acid in the presence of KOH to GHV, with >100,000 TON in 2 h at 150 °C, using 1 ppm catalyst. The most prolific catalyst, [(NHC-SO3-)2(CO)2Ir]Na, can also facilitate transfer hydrogenation from other hydrogen donors, such as 2-propanol, potassium formate, and most notably, ethanol, which can also be derived from renewables. Ethanol is a highly efficient hydrogen donor for levulinic acid using this catalyst, affording >7,000 turnovers in 2 h using 10 ppm catalyst.

Catalytic conversion of HMF into ethyl levulinate – A biofuel over hierarchical zeolites

Catalytic conversion of 5-hydroxymethyl-2-furfuraldehyde (HMF, a biomass-derived platform chemical) into ethyl levulinate (EL) is an attractive approach for producing renewable transport fuels for mitigating global warming. We report here the application of hierarchical zeolites (DZSM-5 and MZSM-5 synthesized by desilication and mesoporous templating approaches, respectively) as solid acid catalysts for this transformation. Hierarchical structure of these zeolites was confirmed by X-ray diffraction, nitrogen-physisorption and electron microscopy, and acidity was determined by temperature-programmed desorption of ammonia. HMF conversion of 94.2% with EL selectivity of 90.8% was achieved over the MZSM-5 catalyst. Acidity, pore size and surface properties affected the catalytic activity.

Highly Selective Conversion of Furfural to Furfural Alcohol or Levulinate Ester in One Pot over ZrO2@SBA-15 and Its Kinetic Behavior

Biorefinery for the purpose of producing biofuels, chemicals, and materials has received much attention. Furfural alcohol (FOL) and levulinate ester (LE) are important biomass-derived platform chemicals, and they are produced from sugar-based furfural (FAL). Unfortunately, the two products are often obtained separately in different reaction systems, which is undesirable; furthermore, it is of significant practical interest to control their selectivity so that the desired product can be accumulated in high yields. Herein, we present an efficient method for the highly selective conversion of FAL to FOL or isopropyl levulinate (IPL) in a one pot system using isopropanol as the hydrogen source and ZrO2@SBA-15 as a bifunctional catalyst with both Lewis acid and Brønsted acid sites. Under optimized reaction conditions, high yields of FOL and IPL in up to 90.4% and 87.2%, respectively, were obtained. Based on the experimental results, a kinetic model describing the catalytic conversion of FAL into FOL and IPL process has been established, which has a good correlation (R2 > 0.92) between the measured and predicted data. The developed kinetics can provide an effective tool to monitor the process and tailor the process conditions to obtain the desired product.

Strategies to Control Electrochemical Hydrogenation and Hydrogenolysis of Furfural and Minimize Undesired Side Reactions

As the availability of biomass-derived feedstocks increases, the infrastructure necessary to upgrade biomass-derived platform chemicals to value-added compounds from distributed point sources needs to be developed. Furfural, a C5-biomass-derived platform chemical, can be converted to a variety of desirable products. By using electrochemical hydrogenation and hydrogenolysis (ECH), furfural can be converted to furfuryl alcohol and 2-methyl furan at ambient conditions using renewable intermittent electricity without needing hydrogen gas supplied to the reactor. It is desired for the ECH of furfural to have high reaction rates (i.e. high currents), high faradaic efficiencies and control of the selectivity between furfuryl alcohol and 2-methyl furan, all while minimizing the undesired side reactions of hydrogen evolution and humins formation. Achieving this balance is challenging. In this viewpoints article the impact of reaction conditions including electrolyte, pH, current density, potential, and reaction du...