HMF Yield Research Articles

Unveiling the catalytic effects of Brønsted acidic ionic liquid on quantitative α-glucose conversion to 5-HMF: Experimental and computational studies

Effective biomass conversion to 5-HMF(5-hydroxymethylfurfural) is still a challenge and needs to be improved because of the 5-HMF importance as building blocks for valuable monomers and fuel precursors. We suggest for the first time utilization of low-cost metal-free Brønsted acidic Ionic liquid (IL) N,N-Diethyl-1,4-phenylenediamine hydrogen sulfate, [DPhDA]HSO4 as a catalyst for the α-glucose dehydration to 5-HMF. Quantitative α-glucose conversion is achieved via optimizing the reaction condition: 91.4% 5-HMF yield with 30 mol% [DPhDA]HSO4 in the presence of DMSO as a solvent at 160 °C in 30 min (TOF 6.1 h−1). 3-fold increase in reaction time leads to higher (94%) 5-HMF yield at 160 °C with lower TOF 1.6 h−1. The IL surprising catalytic performance is scrutinized with its amphiprotic nature (availability of basic and acidic spots in its structure (Fig. 1)). Further computational mechanistic studies revealed the function of the catalytic sites in the α-glucose dehydration. We calculated five-membered ring formation and water extrusion in one concerted transition state (TS2A, ΔG‡ = 38.8 kcal/mol) following the α-glucose ring-opening (TS1, ΔG‡ = 20.4 kcal/mol). Further four steps (sp3-s, C–H bond cleavages (TS3, TS6) and dehydroxylation (TS4A, TS5)) are quite straightforward to reach the product (5-HMF).

Application of vanadyl hydrogen phosphate/KIT-6 composites as a catalyst for dehydration of sucrose

In this research work, the synthesis of well-ordered mesoporous structure KIT-6 silica-supported vanadyl hydrogen phosphate hemihydrate (VHP/KIT-6) catalysts possessing varying surface area was carried out, followed by being utilized in the dehydration of sucrose to 5-hydroxymethylfurfural (5-HMF) as a solid acid catalyst. The fabrication of two different VHP/KIT-6 catalysts was conducted using the impregnation approach through V2O5 reduction in alcoholic media. Then, the catalytic behavior presented by the prepared VHP/KIT-6 samples was compared with unsupported VHP and unsupported vanadyl pyrophosphate (VPP), which was prepared through the calcination of VHP precursor at 400 °C for 24 h. The prepared catalysts were characterized by different analyses, including ICP-OES, BET, XRD, NH3-TPD analysis, FT-IR spectroscopy, as well as SEM and TEM techniques. Furthermore, important parameters, including the catalyst type and weight, sucrose amount, time, temperature, and the type of solvent on sucrose dehydration, were also studied. It was observed that the highest catalytic activity in the dehydration reaction (5-HMF yield: 67%, sucrose conversion: > 94%) could be provided by the catalyst possessing the highest surface area. Moreover, the catalyst reusability was examined for consecutive four times, based on which no considerable change in the catalytic activity was observed.

Efficient microwave-assisted production of furanics and hydrochar from bamboo (Phyllostachys nigra “Boryana”) in a biphasic reaction system: effect of inorganic salts

In this study, a microwave-assisted process was developed for the production of 5-hydroxymethylfurfural (HMF), furfural, and hydrochar from bamboo (Phyllostachys nigra “Boryana”) in a biphasic reaction system. The system consisted of an acidified aqueous phase and methyl isobutyl ketone (MIBK) as the organic phase and enabled the instantaneous extraction of HMF and furfural in the organic phase. In this way, unwanted side and rehydration reactions are avoided. The aim of the study was to maximize HMF and furfural yields from bamboo in short reaction times. Building on previous studies, an HCl concentration of 0.13 M was used to ensure the simultaneous conversion of cellulose and xylan to HMF and furfural, respectively. To shorten the reaction time considerably, higher reaction temperatures were applied in this study (200–240°C). The use of microwave irradiation allowed very short reaction rates for maximum HMF and furfural production. Yields of 21 wt% HMF, 13 wt% furfural, and 39.5 wt% hydrochar were achieved using bamboo culm particles and by applying 0.13 M HCl (10 wt% NaCl) and 220°C with a reaction time of 2 min. The results show that the required reaction time to reach a maximum HMF and furfural yield was not significantly influenced by the particle size (< 200μm–2 mm). The effect of NaCl in the production of HMF and furfural was assessed. It was clear that the addition of NaCl increased the maximum HMF yield but also enhanced the unwanted rehydration reaction to levulinic acid. Results indicated that NaCl could be absorbed on the surface of the hydrochar.

Hierarchical Porous Nitrogen-Doped Carbon Catalyst by the Pickering HIPE Technique: Synthesis and Application in HMF Production

In this paper, water-in-oil (W/O)-type Pickering high-internal phase emulsions (Pickering HIPEs) were stabilized using the modified SBA-15 with appropriate wettability as the stable particle. After thermal polymerization and subsequent sulfonation, we obtained hierarchical porous nitrogen-doped carbon catalysts (SNCs) with acid–base bifunctional active sites. The as-prepared catalysts have hierarchical porous structures, and acidic and basic catalytic activity centers, which can significantly improve the catalytic activity of the conversion of glucose to 5-hydroxymethylfurfural (HMF). The results showed that the highest HMF yield of 61.3% can be obtained, and the recovered catalyst still has a significant catalytic activity after four consecutive cycles. This work offers a versatile strategy for developing nitrogen-doped carbonaceous catalysts for a wide range of biomass transformation to platform chemicals.

5-Hydroxy-2-Methylfurfural from Sugar Beet Thick Juice: Kinetic and Modeling Studies

5-Hydroxy-2-methylfurfural (HMF) has a high derivatization potential and is considered the sleeping giant of biobased platform chemicals. It is accessible by the acid hydrolysis of various carbohydrate-containing feeds, preferably those high in fructose content. We here report a detailed study on the use of thick juice, an intermediate sucrose (SUC)-rich stream in a sugar factory, and pure SUC for the synthesis of HMF in a batch reactor setup [in the presence of water and sulfuric acid (0.01 M) and at 180 °C]. Distinct differences in reactivity were found for both feeds, related to the presence of impurities (i.e., organic acids and salts) in the thick juice. To better understand the effect of the thick juice impurities, detailed model studies were performed involving the use of a model solution of SUC spiked with one of the thick juice impurities (organic acids such as maleic acid and a range of salts with potassium, sodium, calcium, and magnesium as the cations and carbonates, chlorides, and sulfates as the anions). The data were successfully modeled using a kinetic model for the main reactions in the network. The developed model revealed that sulfate anions have a major effect on the HMF yield and the batch time required to reach its optimum and are the likely cause of the differences in reactivity between pure SUC and thick juice.

Leaf-derived sulfonated carbon dots: efficient and recoverable catalysts to synthesize 5-hydroxymethylfurfural from fructose

Sulfonated carbon dots (SCDs) were synthesized from plant leaves via continuously hydrothermal treatment by hydrogen peroxide and sulfuric acid, used as catalyst for converting fructose to 5-hydroxymethylfurfural (HMF). Owing to nanosize effect and moderate acidic intensity, SCDs could thoroughly distribute in the solvent with an improved interfacial compatibility and selectively convert fructose to HMF. Under the optimal condition, the yield of HMF was 92.6% along with a fructose conversion of 100%, benefiting from a low activation energy of 52.9 kJ/mol when dimethylsulfoxide was used as solvent. The SCDs catalyst can be recovered, after six recycles, the fructose conversion and HMF yield were remained 66.1% and 56.2% under condition with incompletely conversion of fructose, respectively. This work provides a sustainable route to prepare carbon dots with a superior catalytic performance for converting biomass to important biobased platform chemicals.

Conversion of Glucose to 5-Hydroxymethylfurfural, Levulinic Acid, and Formic Acid in 1,3-Dibutyl-2-(2-butoxyphenyl)-4,5-diphenylimidazolium Iodide-Based Ionic Liquid

The separation process between 5-hydroxymethylfurfural (HMF) and trace glucose in glucose conversion is important in the biphasic system (aqueous–organic phase), due to the partial solubility property of HMF in water. In addition, the yield of HMF via the dehydration reaction of glucose in water is low (under 50%) with the use of Brønsted acid as a catalyst. Therefore, this study was conducted to optimize the production and separation of products by using a new hydrophobic ionic liquid (IL), which is more selective than water. The new IL (1,3-dibutyl-2-(2-butoxyphenyl)-4,5-diphenyl imidazolium iodide) [DBDIm]I was used as a solvent and was optimized for the dehydration reaction of glucose to make a more selective separation of HMF, levulinic acid (LA), and formic acid (FA). [DBDIm]I showed high performance as a solvent for glucose conversion at 100 °C for 120 min, with a yield of 82.2% HMF, 14.9% LA, and 2.9% FA in the presence of sulfuric acid as the Brønsted acid catalyst.

Synthesis of ordered hierarchically mesoporous/microporous carbon materials via compressed CO2 for fructose-to-HMF transformation

Well-ordered hierarchically mesoporous/microporous carbon materials have been successfully fabricated by using dual soft-templating approach through compressed CO2. Pluronic F127 and different type of surfactants, including nonionic, cationic, and anionic surfactants, were used as dual templates to investigate the influence on the morphology and nanostructure of the as-prepared carbon samples. TEM, SEM, N2 sorption, wide-angle and small-angle XRD analysis were employed to reveal the well-ordered hierarchically micro-mesoporous structure with 2D hexagonal symmetry by using compressed CO2. The prepared HPC samples with different pressures as the catalyst carriers have been functioned by chlorosulfonic acid for the fructose conversion into HMF. Chlorosulfonic acid concentration, catalyst dosage and reaction temperature have been optimized for fructose-to-HMF transformation with the obtained catalyst. The performances of as-made HPC–SO3H samples in HMF yield and reaction rate of fructose-to-HMF transformation have been investigated. The stability of the samples was also conducted in the dehydration of fructose to HMF for five cycles. The possible catalytic mechanism by using hierarchically porous carbon materials as catalyst support for fructose-to-HMF transformation was proposed.

Enhanced conversion of α-cellulose to 5-HMF in aqueous biphasic system catalyzed by FeCl3-CuCl2

This study was to investigate the optimal additions of the cellulose decomposition reaction to obtain the most yield of 5-HMF and other furan derivatives in various biphasic systems with FeCl3-CuCl2 mixed catalysts, and explore its depolymerization kinetics. A series of controllable reactions have been performed under mild environmentally friendly atmosphere. The experiment results showed that 49.13 wt% of 5-HMF was the maximum production along with 2.98 wt% other furan derivatives catalyzed by mixed Lewis acid FeCl3-CuCl2 under the two phases which included high concentration NaCl aqueous phase and n-butanol organic phase at 190 °C for 45 min. The conclusion suggested that two-phase systems benefited the yield of 5-HMF, furan derivatives via extracting the target products from reaction phase to organic phase to avoid rehydration of 5-HMF. The kinetic calculation revealed the conversion with mixed catalysts had lower reaction apparent activation energy (21.65 kJ/mol, 190-230 °C) and the reaction rate was faster than that with acid-based catalysts. Based on experiment exploration, the probable mechanism of cellulose decomposition with FeCl3-CuCl2 was proposed.

Waste Polyethylene terephthalate Derived Carbon Dots for Separable Production of 5-Hydroxymethylfurfural at Low Temperature

Waste Polyethylene terephthalate plastic bottles were used as precursors to fabricate carbon dots (CDs) via air oxidation and sulfuric acid hydrothermal treatment. Owing to the nano-size effect and abundant acidic groups, CDs allowed their application as a novel solid acid for quasi-homogeneous catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF). Under the optimal condition, an ultra-high yield of HMF was 97.4% along with 100% fructose conversion at low temperature of 50 °C when [BMIM]Cl/ethanol was used as solvent. The CDs catalyst also displayed a prominent recyclability and was used for six recycles without massive loss in catalytic activity. Furthermore, 98.6% of HMF could be obtained from final products. The findings provide a novel sustainable route using recyclable plastics to synthesize carbon dots with a superior catalytic performance for conversion of biomass to important bio-based platform chemicals.

Facile depolymerization of microcrystalline cellulose in ionic liquid medium catalyzed by carbon materials as catalysts

This study highlights novel approach for complete utilization of cellulose using metal immobilized modified activated carbon M-ACS and metal immobilized cellulose composite M ​− ​C in ionic liquid medium. Catalytic activity of the system was improved using metal immobilized modified activated carbon with varying impregnation ratios (0.5–25 ​wt%) respectively. Maximum yield of Total reducing sugars (TRS) was 64.68% and 5-Hydroxymethylfurfural (5-HMF) was 54.76% using Chromium immobilized modified activated carbon catalyst (15 ​wt%) in a reaction time of 60 ​min ​at 120 ​°C. Also, Chromium immobilized cellulose composite i.e. Cr–C: 20 ​wt% gave maximum 48.78% (TRS) and 39.67% (5-HMF) yield under similar operating conditions. Results revealed that metal immobilized cellulose composite M ​− ​C also gave appreciable product yield but at a lower rate than M-ACS. Also, the efficacy of cellulose pretreatment was evaluated using acids and results were found to be significant and effective. To understand hydrolysis rate during isomerization and dehydration steps, synthetic glucose and fructose solutions of varying concentration (3–45 ​wt%) were used. Complete utilization of cellulose with suitable acidity of the process has been proposed i.e cellulose solubilization without compromising with 5-HMF yield. Recyclability of catalyst, composite and ionic liquid at 1 ​atm pressure facilitate the economical and feasible production of TRS and 5-HMF. Development of environment friendly and economical ionic liquid/catalyst system can be considered as a potential alternative for the conversion of cellulose to bio-based products.

LiCl-promoted-dehydration of fructose-based carbohydrates into 5-hydroxymethylfurfural in isopropanol.

The carbohydrate-derived 5-hydroxymethylfurfural (HMF) is one of the most versatile intermediate chemicals, and is promising to bridge the growing gap between the supply and demand of energy and chemicals. Developing a low-cost catalytic system will be helpful to the production of HMF in industry. Herein, the commercially available lithium chloride (LiCl) and isopropanol (i-PrOH) are used to construct a cost-effective and low-toxic system, viz., LiCl/i-PrOH, for the preparation of HMF from fructose-based carbohydrates, achieving ∼80% of HMF yield under the optimum conditions. The excellent promotion effect of LiCl on fructose conversion in i-PrOH could be attributed to the synergistic effect of LiCl with i-PrOH through the LiCl-promoted and i-PrOH-aided dehydration process, and the co-operation of LiCl and i-PrOH for stabilizing the as-formed HMF by hydrogen/coordination bonds, giving a low activation energy of 68.68 kJ mol−1 with a pre-exponential factor value of 1.2 × 104 min−1. The LiCl/i-PrOH system is a substrate-tolerant and scalable catalytic system, fructose (scaled up 10 times), sucrose, and inulin also give 73.6%, 30.3%, and 70.3% HMF yield, respectively. Moreover, this system could be reused 8 times without significant loss of activity. The readily available and low-toxic LiCl, the sustainable solvent (i-PrOH), the renewable starting materials, and the mild reaction conditions make this system promising and sustainable for the industrial production of HMF in future.

Direct Synthesis of 5-Hydroxymethylfurfural (HMF) from Cellulose using Saturated Steam

5-Hydroxymethylfurfural (HMF), a compound that can be synthesized from cellulose, has attracted significant attention because it can be converted into various chemical products. Although various methods for the direct conversion of cellulose to HMF using special solvents and catalysts have been reported, they are not desirable in terms of green sustainable chemistry and manufacturing costs. Herein, we report the direct conversion of cellulose to HMF using saturated steam, i.e., water, as an environment-friendly method. We investigated the effects of the molecular weight of cellulose and amount of added water on the yields of glucose and HMF using a batch system. Glucose and HMF yields were improved by using low-molecular-weight cellulose as the raw material and the amount of added water was important for maximizing the HMF yield. The balance of hydrolysis and dehydration was controlled by optimizing the amount of added water, with a maximized HMF yields of 21%. This study demonstrates that saturated steam has great potential to be applied for the direct conversion of cellulose to HMF.

Preparation of SAPO-34-Based Catalyst for Conversion of Fructose to 5-Hydroxymethylfurfural

Solid acid-catalyzed dehydration of fructose to produce 5-hydroxymethylfurfural (5-HMF) has been a hotspot in biomass conversion research in recent years. In this study, a novel SAPO‑34‑based catalyst was prepared by consecutive steps of titanium doping, sulfuric acid impregnation, and sulfonic acid functionalization. Characterization of the catalyst with X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), inductively coupled plasma optical emission spectrometer (ICP-OES), and acid-base titration revealed different pore structures and more acid content compared to SAPO‑34. The catalyst was applied to the preparation of 5-HMF by dehydration of fructose, and the maximum yield (74.0%) of 5-HMF was obtained by reacting in dimethyl sulfoxide (DMSO) at 170 °C for 50 min. In addition, the applicability of the catalytic system to other substrates and the stability of the catalyst after five cycles were investigated, which are valuable for further probing on the concerned aspects.

Tuning Brønsted and Lewis acidity on phosphated titanium dioxides for efficient conversion of glucose to 5-hydroxymethylfurfural.

5-Hydroxymethylfurfural (HMF) derived from cellulosic sugars has become increasingly important as a platform chemical for the biorefinery industry because of its versatility in the conversion to other chemicals. Although HMF can be produced in high yield from fructose dehydration, fructose is rather expensive because it requires multiple processing steps. On the other hand, HMF can be produced directly from highly abundant glucose, which could reduce time and cost. However, an effective and multifunctional catalyst is needed to selectively promote the glucose-to-HMF reaction. In this work, we report a bifunctional phosphated titanium dioxide as an efficient catalyst for such a reaction. The best catalyst exhibits excellent catalytic performance for the glucose conversion to HMF with 72% yield and 83% selectivity in the biphasic system. We achieve this by tuning the solvent system, controlling the amount of Brønsted and Lewis acid sites on the catalyst, and modification of the reaction setup. From the analysis of acid sites, we found that the addition of phosphate group (Brønsted acid site) onto the surface of TiO2 (Lewis acid site) significantly enhanced the HMF yield and selectivity when the optimum ratio of Brønsted and Lewis acid sites is reached. The high catalytic activity, good reusability, and simple preparation method of the catalyst show a promise for the potential use of this catalytic system on an industrial scale.

Selective fructose dehydration to 5-hydroxymethylfurfural from a fructose-glucose mixture over a sulfuric acid catalyst in a biphasic system: Experimental study and kinetic modelling

A two-step process combining the (equilibrium) glucose isomerization to fructose with selective dehydration of fructose in the obtained sugar mixture to 5-hydroxymethylfurfural (HMF), where glucose is largely unconverted and recycled, represents an attractive concept to increase the overall efficiency for HMF synthesis. This work presents experimental and modelling studies on the conversion of such fructose-glucose mixture to HMF using the sulfuric acid catalyst in a water-methyl isobutyl ketone biphasic system under a wide range of conditions (e.g., temperature, catalyst and sugar concentrations). Through detailed product analyses and ESI-MS spectroscopy, the excess formation of formic acid (together with humins) by the direct sugar/HMF degradation was confirmed and included in the reaction network (neglected in most literatures). The kinetic modelling based on batch experiments in monophasic water well describes the measurements thereof, whereas distinct deviations were found in the prediction of typical literature kinetic models. The incorporation of HMF equilibrium extraction into the developed kinetic model, with consideration of phase volume change as a function of temperature and partial phase miscibility, enables to predict reaction results in the biphasic system in batch. This kinetic model allows to optimize conditions for HMF synthesis that are favored in continuous reactors with minimized back mixing. Based on the model implications, the biphasic system was optimized with slug flow microreactors to better address process intensification and scale-up aspects. Using a simulated fructose-glucose mixture feedstock to represent commercially available high fructose corn syrups, a maximum HMF yield of 81% was obtained at 155 °C over 0.05 M H2SO4 at a residence time of 16 min in the microreactor, with 96% fructose conversion and over 95% of glucose remaining unconverted.

Switchable (pH driven) aqueous two-phase systems formed by deep eutectic solvents as integrated platforms for production-separation 5-HMF

The function to induce dynamic-phase shifts between mono/biphasic systems is crucial to separation processes. Switchable (pH driven) ATPS composed of DESs and salts are here disclosed to act as integrated platforms for the production-separation processes. The catalytic carbohydrate conversion to 5-hydroxymethylfurfural (5HMF) was conducted in a homogeneous acidic aqueous-DES medium. Then, the formation of the biphasic region was induced by tailoring the pH of the aqueous homogeneous medium, leading to the complete separation of 5-HMF from the carbohydrate. Herein, the effects of the phase-forming DES species (composed of ethanol/n-propanol and [N4444]Cl), the K3C6H5O7 concentration and pH on the distribution of 5-HMF and fructose in DES-ATPSs were investigated. The optimal composition of the DES-ATPS system was 30 wt% [N4444]Cl:ethanol (1:2) or [N4444]Cl:n-propanol (1:2) and 35 and 40 wt% K3C6H5O7, respectively. The results showed that the integrated platforms have good catalytic effect, and the conversion rate of fructose reached 87.21%, with a 5-HMF yield of 46.76% and 0.1 g of apple peel produced 15.43 mg 5-HMF. The extraction efficiency of the DES-ATPS composed of [N4444]Cl:ethanol (1:2) and [N4444]Cl:n-propanol (1:2) were the highest within 20 min (5-HMF extraction efficiency 98.53% and 98.59%, respectively), which has economic benefits and comprehensiveness.

Experimental and Kinetic Study on the Production of Furfural and HMF from Glucose

Furfural and 5-hydroxymethylfurfural (HMF) have been identified as promising bio-platform furans that have a wide range of potential applications as biofuels, bioplastics, and biochemicals. Furfural and HMF are typically synthesized from the substrates of C5 sugars and C6 sugars, respectively. Furfural can also be produced from C6 sugars, which is technically more challenging owing to the higher energy requirement for carbon–carbon bond cleavage. In this study, the simultaneous production of furfural and HMF from glucose was conducted over different binary catalyst systems of Brønsted acids and Lewis acids using γ-valerolactone (GVL) as the solvent. A promising performance was achieved by a SnSO4-H2SO4 coupling catalyst, with an optimized furfural yield of 42% and an HMF yield of 34% at 443 K in GVL. In addition, a kinetics study was performed in order to understand the mechanism of the simultaneous formation of furfural and HMF from glucose at different temperatures and GVL/water ratios. The results showed that the ratio of furfural to HMF production rate at different temperatures (433 to 463 K) or GVL/water ratios (90 to 80%) was constant close to 1, suggesting that the production of furfural and HMF might follow similar reaction pathways. Finally, the reaction pathway of glucose conversion to furfural and HMF was proposed based on the experimental and kinetics studies.

Phosphotungstic acid on activated carbon: A remarkable catalyst for 5-hydroxymethylfurfural production

Phophotungstic acid (HPW) supported on activated carbon (AC) was prepared and used for dehydration of fructose to 5-hydroxymethylfurfural (HMF), a biomass-derived precursor for chemicals and fuels. Different characterization techniques showed that Keggin structure of HPW was maintained after impregnation process by incipient wetness method with ethanol as solvent. The high mass content of the active phase (50 wt%) on the support resulted in accessible acid sites and high acid density, important for the dehydration reaction. The effects of reaction time, catalyst amount, and temperature were investigated. The catalytic system with dimethyl sulfoxide (DMSO) as solvent provided an efficient transformation of fructose to HMF, resulting in high HMF yields (99.3 %) and total fructose conversion after 30 min of reaction at 140 °C. Fructose conversion was not significantly affected by the catalyst amount. On the other hand, the increase in temperature resulted in greater and faster conversion. HMF yield was deeply affected by all reaction variables. Moreover, HPW/AC was reused five times without significant loss of activity. Additionally, a kinetic evaluation was performed and the activation energy of fructose conversion to HMF was 109.4 kJmol−1.

Simultaneous Direct Production of 5-Hydroxymethylfurfural (HMF) and Furfural from Corncob Biomass Using Porous HSO3-ZSM-5 Zeolite Catalyst

A feasible catalytic process was developed for the simultaneous direct production of 5-hydroxymethylfurfural (HMF) and furfural from corncob biomass using porous HSO₃-ZSM-5 zeolite solid-acid catalyst in organic/water cosolvents. This research work demonstrated and optimized the catalytic performance of sulfonated ZSM-5 zeolite and a highly tunable cosolvent system to significantly improve the coproduction of HMF and furfural from lignocellulosic biomass in a single-phase reaction process by integrating biomass hydrolysis with catalytic dehydration of sugars. The sulfonated ZSM-5 zeolite exhibited high catalytic activity for the corncob biomass conversion to HMF and furfural, the important and useful platform chemicals in the industry. The reaction conditions including solvent, catalyst loading, temperature, and reaction time were investigated. Combining modified ZSM-5 catalyst with the THF/H₂O cosolvent gave high simultaneous yields of HMF (49 ± 0.5%) and furfural (89 ± 0.5%) directly from the corncob biomass with low levulinic acid formation (11%) at suitable reaction conditions.