5‐(Chloromethyl)furfural production from glucose: A pioneer kinetic model development exploring the mechanism

Abstract

Conversion of glucose to 5-(chloromethyl)furfural (CMF) is one of the wellknown high yield unit processes in lignocellulosic biomass valorization. A kinetic modeling study was not reported for the reaction, owing to the complexity in quantification of CMF. Herein we have successfully developed a rapid, sensitive, and specific HPLC method (reverse phase) to quantify the generated CMF (range: 10-650 μg/mL) in a dichloroethane solvent. The Box-Behnken design of experiment method employed for the statistical optimization. A kinetic model was developed based on the homogeneous first-order kinetic model, and the results are in good agreement with the experiment data. The formation of CMF, 5-(hydroxymethyl)furfural, formic acid, levulinic acid, and humins from glucose and HCl were modeled using a serial parallel reaction mechanism. The apparent activation energy (E a ) for glucose decomposition and CMF formation is 99 and 31 kJ/mol. K E Y W O R D S5-(chloromethyl)furfural, design of experiment, glucose dehydration, kinetic model, nonlinear least-squares method

Energy-efficient and eco-friendly continuous production of 5-CMF in a UV-ultrasound irradiated catalytic packed bed reactor: heterogeneous kinetics, reactor simulation and LCA analysis

“…Accordingly, the kinetic rate constants and equilibrium constants for different reactions steps involved in the 5-CMF synthesis process were evaluated and tabulated in Table 5. Finally, the rate constants of the involved reaction steps at different temperatures were used to determine the activation energies (E) and preexponential factors (E 0 ), which align well with the previous studies, 20,21 providing further validation for the accuracy of the findings. The evaluated activation energies for SS hydrolysis, glucose dehydration and 5-HMF chlorination step were 79.04 kJ mol −1 , 61.55 kJ mol −1 and 52.2 kJ mol −1 , respectively.…”

“…Recently, some research studies were reported on the reaction kinetics of the 5-CMF synthesis process in a homogeneous catalytic system. Antonyraj et al 20 presented the first homogeneous kinetic models for the consecutive reaction steps in the 5-CMF synthesis from glucose in a homogeneous catalytic (HCl) system. Another study by Rojahn et al 21 developed homogeneous kinetic models for the consecutive reaction steps in the 5-CMF synthesis from d -fructose.…”

Production and Downstream Integration of 5-(Chloromethyl)furfural from Lignocellulose

“…51 Reaction Parameter Analysis. Mascal et al set the basis 26,28,59,61 for understanding the impact of the reaction parameters that can be varied in the conversion of saccharides to CMF. Parameters with the greatest impact in the course of this reaction are categorized as follows: Hansen solvent parameters, solvent fraction, reaction temperature, acid concentration, reaction time, mass-transfer effect, and initial xylose and/or glucose concentration.…”

“…The reactors were loaded with main hydrolysate (aqueous phase) and the organic solvent of choice from Table in a 1:3 v/v ratio of hydrolysate/organic phase. These screening reactions were carried out in batch at 80 °C and for 3 h based on previous recommendations from Mascal et al ,,, After completion, the reactors were brought to room temperature, and the organic phase was separated for analysis. The CMF yield obtained for each of the solvents screened is shown in Figure .…”

“…The reactors were loaded with main hydrolysate (aqueous phase) and the organic solvent of choice from Table 2 in a 1:3 v/v ratio of hydrolysate/organic phase. These screening reactions were carried out in batch at 80 °C and for 3 h based on previous recommendations from Mascal et al 26 , 28 , 59 , 61 After completion, the reactors were brought to room temperature, and the organic phase was separated for analysis. The CMF yield obtained for each of the solvents screened is shown in Figure 11 .…”