An Integrated Production of Diesel Fuel Precursors from Carbohydrates and 2‐Methylfuran over Sn‐Mont Catalyst

Abstract

Condensation of 5‐(hydroxymethyl)furfural (HMF) with 2‐methylfuran provides precursor of diesel fuel. However, HMF production is critical due to its tedious isolation and purification. Herein, we have developed an integrated process for production of diesel precursors directly from cheap HMF precursors and 2‐methylfuran. This process involves, dehydration of carbohydrates to HMF followed by latter's condensation with 2‐methylfuran to give 5,5′‐((5‐((5‐methylfuran‐2‐yl)methyl)furan‐2‐yl)methylene)bis(2‐methylfuran) (1). Over Sn‐Mont catalyst, in solvents like water, DMSO and C4mimBr the product 1 was produced in negligible yields. The yield of 1 was significantly improved to 36% in formic acid medium. Sn‐Mont facilitates the isomerization of glucose to fructose with its Lewis acid sites and formic acid promotes the dehydration of fructose to a mixture of HMF +5‐(formyloxymethyl)furfural (FMF) which was further treated with 2‐methylfuran in same pot. The product 1 was obtained with 40% and 54% yields from sucrose and fructose, respectively. Using this strategy xylose was converted into 5,5′‐(furan‐2‐ylmethylene)bis(2‐methylfuran) (2) in 25% yield.

3-Bromopyridine-Heterogenized Phosphotungstic Acid for Efficient Trimerization of Biomass-Derived 5-Hydroxymethylfurfural with 2-Methylfuran to C21 Fuel Precursor

“…This further indicated that the deposition of organic moieties is most likely to be the major factor that caused the loss of the catalyst activity. From above experiments, by comparing with previous studies [25,57], 3-BrPyPW was demonstrated to show superior reactivity and stability in the production of MMBM from HMF and 2-MF under the examined reaction conditions in our work.…”

“…Based on the experimental results, the possible reaction pathways were proposed and are shown in Scheme 3. The proposed reaction path was also compared with that of previous work reported by Dutta et al [25] and Shinde et al [57]. As identified by GC/MS, a compound with a molecular weight of 272.1 was formed during the reaction process.…”

Effect of the Solvent in Enhancing the Selectivity to Furan Derivatives in the Catalytic Hydrogenation of Furfural

“…Even with the simplifications introduced in Scheme , it is evident that the control of the selectivity in the catalytic hydrogenation is a key factor to tailor the transformation to the aimed products. Between the products that can be obtained, MF is a relevant target, because shows excellent characteristics as substitute for bioethanol in gasoline, , and could be also used to produce diesel additives. , MF is also used to prepare drugs like atropine, sodium acetate, furadantine, anisodamine and thiamine furan as well as for the synthesis of vitamin B1. Recently, furans, MF in particular, have been described as an elegant way of obtaining biobased aromatic compounds via Diels–Alder intermediates …”

Cascade Synthesis of 5‐(Acetoxymethyl)furfural from Carbohydrates over Sn‐Mont Catalyst

“…SnCl 4 ⋅5H 2 O and montmorillonite was reported for the production of alkyl lactate from triose sugars and HMF from carbohydrates . Very recently, we have converted carbohydrates to condensation products (diesel fuel precursors) via an integrated process using Sn‐Mont and formic acid without isolating furfural intermediates . This approach avoided the tedious isolation and purification of furfural intermediates.…”